Recycle content oxo glycols

ABSTRACT

A recycle content oxo glycol and method of making a recycle content oxo glycol wherein the recycle content is derived directly or indirectly from the cracking of recycle content pyrolysis oil and/or gas. The cracking of the pyrolysis oil can be conducted in a gas furnace or a split furnace.

BACKGROUND OF THE INVENTION

Waste materials, especially non-biodegradable waste materials, cannegatively impact the environment when disposed of in landfills after asingle use. Thus, from an environmental standpoint, it is desirable torecycle as much waste material as possible. However, recycling wastematerials can be challenging from an economic standpoint.

To maximize recycling efficiency, it would be desirable for large-scaleproduction facilities to be able to process feedstocks having recyclecontent originating from a variety of waste materials. Some recyclingefforts involve complicated and detailed segregation of waste streams,which contributes to the increased cost of obtaining streams of recyclewaste content. It would be desirable to establish recycle contentwithout the necessity for sorting down to a single type of plastic orwaste material, or which can tolerate a variety of impurities in wastestreams.

In some cases, it may be difficult to dedicate a product having recyclecontent to a particular customer or downstream synthetic process formaking a derivative of the product, particularly if the recycle contentproduct is a gas or difficult to isolate. It may be difficult tosegregate and distribute a dedicated portion of a gas made exclusivelyfrom a recycle content feedstock since the gas infrastructure iscontinuously fluid and often commingles gas streams from a variety ofsources.

Further, it may be desirable to move away from dependence on naturalgas, ethane, or propane as the sole source for making products such asethylene and propylene and their downstream derivatives.

It is also desirable to synthesize chemical compounds, such as oxoglycols, using existing equipment and processes and without the need toinvest in additional and expensive equipment in order to establish arecycle content in the manufacture of the chemical compound.

Oxo glycols, such as 2,2-dimethyl-1,3-propanediol (also called“neopentyl glycol,” or “NPG”), are important products in organicsynthesis. Formed by the hydroformylation of olefins with synthesis gas,the resulting aldehydes may be further reacted in the presence of acatalyst and optionally hydrogenated to form oxo glycols. Such glycolsmay be used in the synthesis of other chemical components, as well aspaints, lubricants, coatings, and plasticizers. These glycols are alsoused as monomers in the formation of polymers, such as polyesters, andwhen so used impart desirable properties to the polymer, such asimproved stability and melt characteristics.

It would be desirable to be able to determine the amount and timing ofestablishing recycle content in a chemical compound such as oxo glycols.Also, there may be a desire to provide an oxo glycol, at certain timesor for different batches, with more or less recycle content or norecycle content. The flexibility in this approach without the need toadd significant assets is desirable.

SUMMARY OF THE INVENTION

There is now provided a method of obtaining a recycle content oxo glycolcomposition, methods of reacting recycle content olefin and/or aldehydeor applying a recycle content value to make a recycle content oxoglycol, uses thereof, compositions thereof, and systems thereof, each asfurther described in the claims and detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an illustrate of a process for employing a recycle contentpyrolysis oil composition (r-pyoil) to make one or more recycle contentcompositions into r-compositions.

FIG. 2 is an illustration of an exemplary pyrolysis system to at leastpartially convert one or more recycled waste, particularly recycledplastic waste, into various useful r-products.

FIG. 3 is a schematic depiction of pyrolysis treatment throughproduction of olefin containing products.

FIG. 4 is a block flow diagram illustrating steps associated with thecracking furnace and separation zones of a system for producing anr-composition obtained from cracking r-pyoil and non-recycle crackerfeed.

FIG. 5 is a schematic diagram of a cracker furnace suitable forreceiving r-pyoil.

FIG. 6 illustrates a furnace coil configuration having multiple tubes.

FIG. 7 illustrates a variety of feed locations for r-pyoil into acracker furnace.

FIG. 8 illustrates a cracker furnace having a vapor-liquid separator.

FIG. 9 is a block diagram illustrating the treatment of a recyclecontent furnace effluent.

FIG. 10 illustrates a fractionation scheme in a Separation section,including a demethanizer, dethanizer, depropanizer, and thefractionation columns to separate and isolate the main r-compositions,including r-propylene, r-ethylene, r-butylene, and others.

FIG. 11 illustrates the laboratory scale cracking unit design.

FIG. 12 illustrates design features of a plant-based trial feedingr-pyoil to a gas fed cracker furnace.

FIG. 13 is a graph of the boiling point curve of a r-pyoil having 74.86%C8+, 28.17% C15+, 5.91% aromatics, 59.72% paraffins, and 13.73%unidentified components by gas chromatography analysis.

FIG. 14 is a graph of the boiling point curve of a r-pyoil obtained bygas chromatography analysis.

FIG. 15 is a graph of the boiling point curve of a r-pyoil obtained bygas chromatography analysis.

FIG. 16 is a graph of the boiling point curve of a r-pyoil distilled ina lab and obtained by chromatography analysis.

FIG. 17 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 350° C., 50% boiling between 95° C. and200° C., and at least 10% boiling by 60° C.

FIG. 18 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 150° C., 50% boiling between 80° C. and145° C., and at least 10% boiling by 60° C.

FIG. 19 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 350° C., at least 10% by 150° C., and50% boiling between 220° C. and 280° C.

FIG. 20 is a graph of the boiling point curve of r-pyoil distilled inlab with 90% boiling between 250-300° C.

FIG. 21 is a graph of the boiling point curve of r-pyoil distilled inlab with 50% boiling between 60-80° C.

FIG. 22 is a graph of the boiling point curve of r-pyoil distilled inlab with 34.7% aromatic content.

FIG. 23 is a graph of the boiling point curve of r-pyoil with an initialboiling point of about 40° C.

FIG. 24 is a graph of the carbon distribution of pyoil used in a planttest.

FIG. 25 is a graph of the carbon distribution of pyoil used in a planttest.

FIG. 26 is a schematic depiction of a system suitable for forming arecycle content neopentyl glycol (r-NPG).

DETAILED DESCRIPTION OF THE INVENTION

The word “containing” and “including” is synonymous with comprising.When a numerical sequence is indicated, it is to be understood that eachnumber is modified the same as the first number or last number in thenumerical sequence or in the sentence, e.g. each number is “at least,”or “up to” or “not more than” as the case may be; and each number is inan “or” relationship. For example, “at least 10, 20, 30, 40, 50, 75 wt.% . . . ” means the same as “at least 10 wt. %, or at least 20 wt. %, orat least 30 wt. %, or at least 40 wt. %, or at least 50 wt. %, or atleast 75 wt. %,” etc.; and “not more than 90 wt. %, 85, 70, 60 . . . ”means the same as “not more than 90 wt. %, or not more than 85 wt. %, ornot more than 70 wt. % . . . ” etc.; and “at least 1%, 2%, 3%, 4%, 5%,6%, 7%, 8%, 9% or 10% by weight . . . ” means the same as “at least 1wt. %, or at least 2 wt. %, or at least 3 wt. % . . . ” etc.; and “atleast 5, 10, 15, 20 and/or not more than 99, 95, 90 weight percent”means the same as “at least 5 wt. %, or at least 10 wt. %, or at least15 wt. % or at least 20 wt. % and/or not more than 99 wt. %, or not morethan 95 wt. %, or not more than 90 weight percent . . . ” etc.; or “atleast 500, 600, 750° C. . . . ” means the same as “at least 500° C., orat least 600° C., or at least 750° C. . . . ” etc.

In aspects, methods for making a recycle oxo glycol (“r-OG”) areprovided that start with feeding a recycle content olefin composition atleast a portion of which is derived directly or indirectly frompyrolyzing a recycled waste to a reactor, reacting the olefin withsyngas to produce a recycle content aldehyde (“r-AD”), and then reactingat least a portion of the r-AD in the presence of a catalyst (optionallysubjecting the r-AD to catalytic hydrogenation) to provide an effluentcomprising r-oxo glycol.

Pyrolysis/Cracking Systems and Processes

All concentrations or amounts are by weight unless otherwise stated. An“olefin-containing effluent” is the furnace effluent obtained bycracking a cracker feed containing r-pyoil. A “non-recycleolefin-containing effluent” is the furnace effluent obtained by crackinga cracker feed that does not contain r-pyoil. Units on hydrocarbon massflow rate, MF1, and MF2 are in kilo pounds/hr (klb/hr), unless otherwisestated as a molar flow rate.

As used herein, “containing” and “including” are open ended andsynonymous with “comprising.”

The term “recycle content” is used herein i) as a noun to refer to aphysical component (e.g., compound, molecule, or atom) at least aportion of which is derived directly or indirectly from recycled wasteor ii) as an adjective modifying a particular composition (e.g., acompound, polymer, feedstock, product, or stream) at least a portion ofwhich is directly or indirectly derived from recycled waste.

As used herein, “recycle content composition,” “recycle composition,”and “r-composition” mean a composition having recycle content.

The term “pyrolysis recycle content” is used herein i) as a noun torefer to a physical component (e.g., compound, molecule, or atom) atleast a portion of which is derived directly or indirectly from thepyrolysis of recycled waste or ii) as an adjective modifying aparticular composition (e.g., a feedstock, product, or stream) at leasta portion of which is directly or indirectly derived from the pyrolysisof recycled waste. For example, pyrolysis recycle content can bedirectly or indirectly derived from recycle content pyrolysis oil,recycle content pyrolysis gas, or the cracking of recycle contentpyrolysis oil such as through thermal steam crackers or fluidizedcatalytic crackers.

As used herein, “pyrolysis recycle content composition,” “pyrolysisrecycle composition,” and “pr-composition” mean a composition (e.g., acompound, polymer, feedstock, product, or stream) having pyrolysisrecycle content. A pr-composition is a subset of a r-composition, whereat least a portion of the recycle content of the r-composition isderived directly or indirectly from the pyrolysis of recycled waste.

As used herein, a composition (e.g., compound, polymer, feedstock,product, or stream) “directly derived” or “derived directly” fromrecycled waste has at least one physical component that is traceable torecycled waste, while a composition (e.g., a compound, polymer,feedstock, product, or stream) “indirectly derived” or “derivedindirectly” from recycled waste has associated with it a recycle contentallotment and may or may not contain a physical component that istraceable to recycled waste.

As used herein, a composition (e.g., compound, polymer, feedstock,product, or stream) “directly derived” or “derived directly” from thepyrolysis of recycled waste has at least one physical component that istraceable to the pyrolysis of recycled waste, while a composition (e.g.,a compound, polymer, feedstock, product, or stream) “indirectly derived”or “derived indirectly” from the pyrolysis of recycled waste hasassociated with it a recycle content allotment and may or may notcontain a physical component that is traceable to the pyrolysis ofrecycled waste.

As used herein, “pyrolysis oil” or “pyoil” mean a composition of matterthat is liquid when measured at 25° C. and 1 atm and at least a portionof which is obtained from pyrolysis.

As used herein, “recycle content pyrolysis oil,” “recycle pyoil,”“pyrolysis recycle content pyrolysis oil” and “r-pyoil”” mean pyoil, atleast a portion of which is obtained from pyrolysis, and having recyclecontent.

As used herein, “pyrolysis gas” and “pygas” mean a composition of matterthat is gas when measured at 25° C. and 1 atm and at least a portion ofwhich is obtained from pyrolysis.

As used herein, “recycle content pyrolysis gas,” “recycle pygas,”“pyrolysis content pyrolysis gas” and “r-pygas” mean pygas, at least aportion of which is obtained from pyrolysis, and having recycle content.

As used herein, “Et” is ethylene composition (e.g., a feedstock,product, or stream) and “Pr” is propylene composition (e.g., afeedstock, product, or stream).

As used herein, “recycle content ethylene,” “r-ethylene” and “r-Et” 0having recycle content; and “recycle content propylene,” “r-propylene”and “r-Pr” mean Pr having recycle content.

As used herein, “pyrolysis recycle content ethylene” and “pr-Et” meanr-Et having pyrolysis recycle content; and “pyrolysis recycle contentpropylene” and “pr-Pr” mean r-Pr having pyrolysis recycle content.

As used herein, “AD” is an aldehyde composition (e.g., a feedstock,product, or stream).

As used herein, a “recycle content aldehyde” and “r-AD” mean AD havingrecycle content.

As used herein, a “pyrolysis content aldehyde” and “pr-AD” mean r-ADhaving pyrolysis recycle content.

As used herein, “OG” is oxo glycol composition, e.g., neopentyl glycol(e.g., a feedstock, product, or stream).

As used herein, a “recycle content OG” and “r-OG” mean OG having recyclecontent.

As used herein, a “pyrolysis content OG” and “pr-OG” mean r-OG havingpyrolysis recycle content.

As used throughout, the generic description of the compound, compositionor stream does not require the presence of its species, but also doesnot exclude and may include its species. For example, a “OG” or “any OG”can include oxo glycol made by any process and may or may not containrecycle content and may or may not be made from non-recycle contentfeedstocks or from recycle content feedstocks, and may or may notinclude r-OG or pr-OG. Likewise, r-OG may or may not include pr-OG,although the mention of r-OG does require it to have recycle content. Inanother example, an “Et” or “any Et” can include ethylene made by anyprocess and may or may not have recycle content, and may or may notinclude r-Et or pr-Et. Likewise, r-Et may or may not include pr-Et,although the mention of r-Et does require it to have recycle content.This would apply in similar fashion to Pr, r-Pr and pr-Pr.

“Pyrolysis recycle content” is a specific subset/type (species) of“recycle content” (genus). Wherever “recycle content” and “r-” are usedherein, such usage should be construed as expressly disclosing andproviding claim support for “pyrolysis recycle content” and “pr-,” evenif not expressly so stated. For example, whenever the term “recyclecontent oxo glycol” or “r-OG” is used herein, it should be construed asalso expressly disclosing and providing claim support for “pyrolysisrecycle content oxo glycol” and “pr-OG.”

As used throughout, whenever a cracking of r-pyoil is mentioned, suchcracking can be conducted by a thermal cracker, or a thermal steamcracker, in a liquids fed furnace, or in a gas fed furnace, or in anycracking process. In one embodiment or in combination with any of thementioned embodiments, the cracking is not catalytic or is conducted inthe absence of an added catalyst or is not a fluidized catalyticcracking process.

As used throughout, whenever mention is made of pyrolysis of recyclewaste, or r-pyoil, all embodiments also include (i) the option ofcracking the effluent of pyrolyzing recycle waste or cracking r-pyoiland/or (ii) the option of cracking the effluent or r-pyoil as a feed toa gas fed furnace or to the tubes of gas furnace/cracker.

As used throughout, a “Family of Entities” means at least one person orentity that directly or indirectly controls, is controlled by, or isunder common control with another person or entity, where control meansownership of at least 50% of the voting shares, or shared management,common use of facilities, equipment, and employees, or family interest.As used throughout, the mention of a person or entity provides claimsupport for and includes any person or entity among the Family ofEntities.

In an embodiment or in combination with any other mentioned embodiments,the mention of r-olefin (e.g., r-Et or r-Pr) also includes pr-Et orpr-Pr, or pr-Et or pr-Pr obtained directly or indirectly from thecracking of r-pyoil or obtained from r-pygas; and r-OG also includespr-OG, or pr-OG obtained directly or indirectly from the cracking ofr-pyoil or obtained from r-pygas.

In one embodiment or in combination with any of the mentionedembodiments, there is provided a method for making a r-OG composition byreacting AD (e.g., a AD composition) with hydrogen. The AD can be a r-ADor a pr-AD or a dr-AD. In one embodiment, the method for making a r-OGstarts with feeding r-AD to a reactor for making OG. In embodiments, theAD composition can be made by reacting syngas (CO and hydrogen) with anolefin, e.g., Et or Pr. The olefin can be a r-olefin or a pr-olefin or adr-olefin. In one embodiment, the AD is an r-AD made by feeding r-olefin(e.g., r-Et or r-Pr) to a reactor for making AD.

FIG. 1 is a schematic depiction illustrating an embodiment or incombination with any embodiment mentioned herein of a process foremploying a recycle content pyrolysis oil composition (r-pyoil) to makeone or more recycle content compositions (e.g. ethylene, propylene,butadiene, hydrogen, and/or pyrolysis gasoline): the r-composition.

As shown in FIG. 1, recycled waste can be subjected to pyrolysis inpyrolysis unit 10 to produce a pyrolysis product/effluent comprising arecycle content pyrolysis oil composition (r-pyoil). The r-pyoil can befed to a cracker 20, along with a non-recycle cracker feed (e.g.,propone, ethane, and/or natural gasoline). A recycle content crackedeffluent (r-cracked effluent) can be produced from the cracker and thensubjected to separation in a separation train 30. In an embodiment or incombination with any embodiment mentioned herein, the r-composition canbe separated and recovered from the r-cracked effluent. The r-propylenestream can contain predominantly propylene, while the r-ethylene streamcan contain predominately ethylene.

As used herein, a furnace includes the convection zone and the radiantzone. A convection zone includes the tubes and/or coils inside theconvection box that can also continue outside the convection boxdownstream of the coil inlet at the entrance to the convection box. Forexample, as shown in FIG. 5, the convection zone 310 includes the coilsand tubes inside the convection box 312 and can optionally extend or beinterconnected with piping 314 outside the convection box 312 andreturning inside the convection box 312. The radiant zone 320 includesradiant coils/tubes 324 and burners 326. The convection zone 310 andradiant zone 320 can be contained in a single unitary box, or inseparate discrete boxes. The convection box 312 does not necessarilyhave to be a separate discrete box. As shown in FIG. 5, the convectionbox 312 is integrated with the firebox 322.

Unless otherwise specified, all component amounts provided herein (e.g.for feeds, feedstocks, streams, compositions, and products) areexpressed on a dry basis.

As used herein, a “r-pyoil” or “r-pyrolysis oil” are interchangeable andmean a composition of matter that is liquid when measured at 25° C. and1 atm, at least a portion of which is obtained from the pyrolysis, andwhich has recycle content. In embodiments, at least a portion of thecomposition is obtained from the pyrolysis of recycled waste (e.g.,waste plastic or waste stream).

In embodiments, the “r-ethylene” can be a composition comprising: (a)ethylene obtained from cracking of a cracker feed containing r-pyoil, or(b) ethylene having a recycle content value attributed to at least aportion of the ethylene; and the “r-propylene” can be a compositioncomprising (a) propylene obtained from cracking of a cracker feedcontaining r-pyoil, or (b) propylene having a recycle content valueattributed to at least a portion of the propylene.

Reference to a “r-ethylene molecule” means ethylene molecule deriveddirectly or indirectly from recycled waste and reference to a“pr-ethylene molecule” means ethylene molecule derived directly orindirectly from r-pyrolysis effluent (e.g., r-pyoil and/or r-pygas).

As used herein, a “Site” means a largest continuous geographicalboundary owned by an OG manufacturer, or by one person or entity, orcombination of persons or entities, among its Family of Entities,wherein the geographical boundary contains one or more manufacturingfacilities at least one of which is OG manufacturing facility.

As used herein, the term “predominantly” means more than 50 percent byweight, unless expressed in mole percent, in which case it means morethan 50 mole %. For example, a predominantly propane stream,composition, feedstock, or product is a stream, composition, feedstock,or product that contains more than 50 weight percent propane, or ifexpressed as mole %, means a product that contains more than 50 mole %propane.

As used herein, a composition that is “directly derived” from crackingr-pyoil has at least one physical component that is traceable to anr-composition at least a portion of which is obtained by or with thecracking of r-pyoil, while a composition that is “indirectly derived”from cracking r-pyoil has associated with it a recycle content allotmentand may or may not contain a physical component that is traceable to anr-composition at least a portion of which is obtained by or with thecracking of r-pyoil.

As used herein, “recycle content value” and “r-value” mean a unit ofmeasure representative of a quantity of material having its origin inrecycled waste. The r-value can have its origin in any type of recycledwaste processed in any type of process.

As used herein, the term “pyrolysis recycle content value” and“pr-value” mean a unit of measure representative of a quantity ofmaterial having its origin in the pyrolysis of recycled waste. Thepr-value is a specific subset/type of r-value that is tied to thepyrolysis of recycled waste. Therefore, the term r-value encompasses,but does not require, a pr-value.

The particular recycle content value (r-value or pr-value) can be bymass or percentage or any other unit of measure and can be determinedaccording to a standard system for tracking, allocating, and/orcrediting recycle content among various compositions. A recycle contentvalue can be deducted from a recycle content inventory and applied to aproduct or composition to attribute recycle content to the product orcomposition. A recycle content value does not have to originate frommaking or cracking r-pyoil unless so stated. In one embodiment or incombination with any mentioned embodiments, at least a portion of ther-pyoil from which an allotment is obtained is also cracked in acracking furnace as described throughout the one or more embodimentsherein.

In one embodiment or in combination with any mentioned embodiments, atleast a portion of the recycle content allotment or allotment or recyclecontent value deposited into a recycle content inventory is obtainedfrom r-pyoil. Desirably, at least 60%, or at least 70%, or at least 80%,or at least 90% or at least 95%, or up to 100% of the:

-   -   a. allotments or    -   b. deposits into a recycle content inventory, or    -   c. recycle content value in a recycle content inventory, or    -   d. recycle content value applied to compositions to make a        recycle content product, intermediate, or article (Recycle PIA)        are obtained from r-pyoil.

A Recycle PIA is a product, intermediate or article which can includecompounds or compositions containing compounds or polymers, and/or anarticle having an associated recycle content value. A PIA does not havea recycle content value associated with it. A PIA includes, and is notlimited to, aldehyde, or a OG such as neopentyl glycol.

As used herein, “recycle content allotment” or “allotment” means arecycle content value that is:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from recycled waste or which has a recycle        content value at least a portion of which originates from        recycled waste, optionally originating from r-pyoil, to a        receiving composition (the composition receiving the allotment,        e.g., compound, polymer, feedstock, product, or stream) that may        or may not have a physical component that is traceable to a        composition at least a portion of which is obtained from        recycled waste; or    -   b. deposited into a recycle inventory from an originating        composition (e.g., compound, polymer, feedstock, product, or        stream) at least a portion of which is obtained from or having a        recycle content value or pr-value at least a portion of which        originates from recycled waste.

As used herein, “pyrolysis recycle content allotment” and “pyrolysisallotment” or “pr-allotment” mean a pyrolysis recycle content value thatis:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from the pyrolysis of recycled waste or which        has a recycle content value at least a portion of which        originates from the pyrolysis of recycled waste, to a receiving        composition (e.g., compound, polymer, feedstock, product,        article or stream) that may or may not have a physical component        that is traceable to a composition at least a portion of which        is obtained from the pyrolysis of recycled waste; or    -   b. deposited into a recycle inventory from an originating        composition (e.g., compound, polymer, feedstock, product, or        stream) at least a portion of which is obtained from or having a        recycle content value at least a portion of which originates        from the pyrolysis of recycled waste.

A pyrolysis recycle content allotment is a specific type of recyclecontent allotment that is tied to the pyrolysis of recycled waste.Therefore, the term recycle content allotment encompasses pyrolysisrecycle content allocation.

In one embodiment or in combination with any of the mentionedembodiments, a pyrolysis recycle content allotment or pyrolysisallotment may have a recycle content value that is:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from the cracking (e.g. liquid or gas thermal        steam cracking) of r-pyoil, or transferred from recycle waste        used to make r-pyoil that is cracked, or transferred from        r-pyoil that is or will be cracked, or which has a recycle        content value at least a portion of which originates from the        cracking (e.g. liquid or gas thermal steam cracking) of r-pyoil,        to a receiving composition (e.g., compound, polymer, feedstock,        product, or stream or PIA) that may or may not have a physical        component that is traceable to a composition at least a portion        of which is obtained from the cracking of r-pyoil; or    -   b. deposited into a recycle content inventory and is obtained        from a composition (e.g., compound, polymer, feedstock, product,        or stream) at least a portion of which is obtained from or        having a recycle content value at least a portion of which        originates from the cracking (e.g. liquid or gas thermal steam        cracking) of r-pyoil (whether or not the r-pyoil is cracked at        the time of depositing the allotment into the recycle content        inventory provided the r-pyoil from which the allotment is taken        is ultimately cracked).

An allotment can be an allocation or a credit.

A recycle content allotment can include a recycle content allocation ora recycle content credit obtained with the transfer or use of a rawmaterial. In one embodiment or in combination with any of the mentionedembodiments, the composition receiving the recycle content allotment canbe a non-recycle composition, to thereby convert the non-recyclecomposition to an r-composition.

As used herein, “non-recycle” means a composition (e.g., compound,polymer, feedstock, product, or stream) none of which was directly orindirectly derived from recycled waste.

As used herein, a “non-recycle feed” in the context of a feed to thecracker or furnace means a feed that is not obtained from a recycledwaste stream. Once a non-recycle feed obtains a recycle contentallotment (e.g. either through a recycle content credit or recyclecontent allocation), the non-recycle feed become a recycle content feed,composition, or Recycle PIA.

As used herein, the term “recycle content allocation” is a type ofrecycle content allotment, where the entity or person supplying acomposition sells or transfers the composition to the receiving personor entity, and the person or entity that made the composition has anallotment at least a portion of which can be associated with thecomposition sold or transferred by the supplying person or entity to thereceiving person or entity. The supplying entity or person can becontrolled by the same entity or person(s), or Family of Entities, or adifferent Family of Entities. In embodiments, a recycle contentallocation travels with a composition and with the downstream derivatesof the composition. In embodiments, an allocation may be deposited intoa recycle content inventory and withdrawn from the recycle contentinventory as an allocation and applied to a composition to make anr-composition or a Recycle PIA.

As used herein, “recycle content credit” and “credit” mean a type ofrecycle content allotment, where the allotment is not restricted to anassociation with compositions made from cracking r-pyoil or theirdownstream derivatives, but rather have the flexibility of beingobtained from r-pyoil and (i) applied to compositions or PIA made fromprocesses other than cracking feedstocks in a furnace, or (ii) appliedto downstream derivatives of compositions, through one or moreintermediate feedstocks, where such compositions are made from processesother than cracking feedstocks in a furnace, or (iii) available for saleor transfer to persons or entities other than the owner of theallotment, or (iv) available for sale or transfer by other than thesupplier of the composition that is transferred to the receiving entityor person. For example, an allotment can be a credit when the allotmentis taken from r-pyoil and applied by the owner of the allotment to a BTXcomposition, or cuts thereof, made by said owner or within its Family ofEntities, obtained by refining and fractionation of petroleum ratherthan obtained by cracker effluent products; or it can be a credit if theowner of the allotment sells the allotment to a third party to allow thethird party to either re-sell the product or apply the credit to one ormore of a third party's compositions.

A credit can be available for sale or transfer or use, or can be sold ortransferred or used, either:

-   -   a. without the sale of a composition, or    -   b. with the sale or transfer of a composition but the allotment        is not associated with the sale or transfer of the composition,        or    -   c. is deposited into or withdrawn from a recycle content        inventory that does not track the molecules of a recycle content        feedstock to the molecules of the resulting compositions which        were made with the recycle content feedstocks, or which does        have such tracking capability but which did not track the        particular allotment as applied to a composition.

In one embodiment or in combination with any of the mentionedembodiments, an allotment may be deposited into a recycle contentinventory, and a credit or allocation may be withdrawn from theinventory and applied to a composition. This would be the case where anallotment is created by making a first composition from the pyrolysis ofrecycle waste, or from r-pyoil or the cracking of r-pyoil, or by anyother method of making a first composition from recycle waste,depositing the allocation associated with such first composition into arecycle content inventory, and deducting a recycle content value fromthe recycle content inventory and applying it to a second compositionthat is not a derivate of the first composition or that was not actuallymade by the first composition as a feedstock. In this system, one neednot trace the source of a reactant back to the cracking of pyoil or backto any atoms contained in an olefin-containing effluent, but rather canuse any reactant made by any process and have associated with suchreactant a recycle content allotment.

In one embodiment or in combination with any mentioned embodiments, acomposition receiving an allotment is used as a feedstock to makedownstream derivatives of the composition, and such composition is aproduct of cracking a cracker feedstock in a cracker furnace. In oneembodiment or in combination with any mentioned embodiments, there isprovided a process in which:

-   -   a. a r-pyoil is obtained,    -   b. a recycle content value (or allotment) is obtained from the        r-pyoil and        -   i. deposited into a recycle content inventory, and an            allotment (or credit) is withdrawn from the recycle content            inventory and applied to any composition to obtain a            r-composition, or        -   ii. applied directly to any composition, without depositing            into a recycle content inventory, to obtain an            r-composition; and    -   c. at least a portion of the r-pyoil is cracked in a cracker        furnace, optionally according to any of the designs or processes        described herein; and    -   d. optionally at least a portion of the composition in step b.        originates from a cracking a cracker feedstock in a cracker        furnace, optionally the composition having been obtained by any        of the feedstocks, including r-pyoil, and methods described        herein.

The steps b. and c. do not have to occur simultaneously. In oneembodiment or in combination with any mentioned embodiments, they occurwithin a year of each other, or within six (6) months of each other, orwithin three (3) months of each other, or within one (1) month of eachother, or within two (2) weeks of each other, or within one (1) week ofeach other, or within three (3) days of each other. The process allowsfor a time lapse between the time an entity or person receiving ther-pyoil and creating the allotment (which can occur upon receipt orownership of the r-pyoil or deposit into inventory) and the actualprocessing of the r-pyoil in a cracker furnace.

As used herein, “recycle content inventory” and “inventory” mean a groupor collection of allotments (allocations or credits) from which depositsand deductions of allotments in any units can be tracked. The inventorycan be in any form (electronic or paper), using any or multiple softwareprograms, or using a variety of modules or applications that together asa whole tracks the deposits and deductions. Desirably, the total amountof recycle content withdrawn (or applied to compositions) does notexceed the total amount of recycle content allotments on deposit in therecycle content inventory (from any source, not only from cracking ofr-pyoil). However, if a deficit of recycle content value is realized,the recycle content inventory is rebalanced to achieve a zero orpositive recycle content value available. The timing for rebalancing canbe either determined and managed in accordance with the rules of aparticular system of accreditation adopted by the olefin-containingeffluent manufacturer or by one among its Family of Entities, oralternatively, is rebalanced within one (1) year, or within six (6)months, or within three (3) months, or within one (1) month of realizingthe deficit. The timing for depositing an allotment into the recyclecontent inventory, applying an allotment (or credit) to a composition tomake a r-composition, and cracking r-pyoil, need not be simultaneous orin any particular order. In one embodiment or in combination with anymentioned embodiments, the step of cracking a particular volume ofr-pyoil occurs after the recycle content value or allotment from thatvolume of r-pyoil is deposited into a recycle content inventory.Further, the allotments or recycle content values withdrawn from therecycle content inventory need not be traceable to r-pyoil or crackingr-pyoil, but rather can be obtained from any waste recycle stream, andfrom any method of processing the recycle waste stream. Desirably, atleast a portion of the recycle content value in the recycle contentinventory is obtained from r-pyoil, and optionally at least a portion ofr-pyoil, are processed in the one or more cracking processes asdescribed herein, optionally within a year of each other and optionallyat least a portion of the volume of r-pyoil from which a recycle contentvalue is deposited into the recycle content inventory is also processedby any or more of the cracking processes described herein.

The determination of whether a r-composition is derived directly orindirectly from recycled waste is not on the basis of whetherintermediate steps or entities do or do not exist in the supply chain,but rather whether at least a portion of the r-composition that is fedto the reactor for making an end product such as AD or OG can be tracedto an r-composition made from recycled waste.

The determination of whether a pr-composition is derived directly orindirectly from the pyrolysis of recycled waste (e.g., from the crackingof r-pyoil or from r-pygas) is not on the basis of whether intermediatesteps or entities do or do not exist in the supply chain, but ratherwhether at least a portion of the pr-composition that is fed to thereactor for making an end product such as OG can be traced to apr-composition made from the pyrolysis of recycled waste.

As noted above, the end product is considered to be directly derivedfrom cracking r-pyoil or from recycled waste if at least a portion ofthe reactant feedstock used to make the product can be traced back,optionally through one or more intermediate steps or entities, to atleast a portion of the atoms or molecules that make up an r-compositionproduced from recycled waste or the cracking of r-pyoil fed to acracking furnace or as an effluent from the cracking furnace.

The r-composition as an effluent may be in crude form that requiresrefining to isolate the particular r-composition. The r-compositionmanufacturer can, typically after refining and/or purification andcompression to produce the desired grade of the particularr-composition, sell such r-composition to an intermediary entity whothen sells the r-composition, or one or more derivatives thereof, toanother intermediary for making an intermediate product or directly tothe product manufacturer. Any number of intermediaries and intermediatederivates can be made before the final product is made.

The actual r-composition volume, whether condensed as a liquid,supercritical, or stored as a gas, can remain at the facility where itis made, or can be shipped to a different location, or held at anoff-site storage facility before utilized by the intermediary or productmanufacturer. For purposes of tracing, once an r-composition made fromrecycled waste (e.g., by cracking r-pyoil or from r-pygas) is mixed withanother volume of the composition (e.g. r-ethylene mixed withnon-recycle ethylene), for example in a storage tank, salt dome, orcavern, then the entire tank, dome, or cavern at that point becomes ar-composition source, and for purposes of tracing, withdrawal from suchstorage facility is withdrawing from an r-composition source until suchtime as when the entire volume or inventory of the storage facility isturned over or withdrawn and/or replaced with non-recycle compositionsafter the r-composition feed to the tank stops. Likewise, this appliesalso to any downstream storage facilities for storing the derivatives ofthe r-compositions, such as r-Et or r-Pr and pr-Et or pr-Prcompositions.

An r-composition is considered to be indirectly derived from recycledwaste or pyrolysis of recycled waste or cracking of r-pyoil if it hasassociated with it a recycle content allotment and may or may notcontain a physical component that is traceable to an r-composition atleast a portion of which is obtained from recycled waste/pyrolysis ofrecycled waste/cracking of r-pyoil. For example, the (i) manufacturer ofthe product can operate within a legal framework, or an associationframework, or an industry recognized framework for making a claim to arecycle content through, for example, a system of credits transferred tothe product manufacturer regardless of where or from whom ther-composition, or derivatives thereof, or reactant feedstocks to makethe product, is purchased or transferred, or (ii) a supplier of ther-composition or a derivate thereof (“supplier”) operates within anallotment framework that allows for associating or applying a recyclecontent value or pr-value to a portion or all of an olefin-containingeffluent or a compound within an olefin-containing effluent or derivatethereof to make an r-composition, and to transfer the recycle contentvalue or allotment to the manufacturer of the product or anyintermediary who obtains a supply of r-composition from the supplier. Inthis system, one need not trace the source of olefin volume back to themanufacture of r-composition from recycled waste/pyrolyzed recycledwaste, but rather can use any olefin composition made by any process andhave associated with such olefin composition a recycle contentallotment, or an r-AD or r-OG manufacturer need not trace the source ofr-olefin or r-AD or r-OG feedstocks, respectively to a compositionobtained by cracking r-pyoil or pyrolized recycle waste, but rather canuse any olefin (e.g., ethylene or propylene) or AD obtained from anysource as a feedstock to make AD or OG, respectively and have associatedwith such AD or OG a recycle content allotment to make r-AD or r-OG.

Examples of how an olefin composition for making AD (and ultimately OG)can obtain recycle content include:

-   -   (i) a cracker facility in which the r-olefin (e.g. r-ethylene)        is made at the facility, by cracking r-pyoil or obtained from        r-pygas, can be in fluid communication, continuously or        intermittently and directly or indirectly through intermediate        facilities, with an olefin-derived petrochemical (e.g. AD or OG)        formation facility (which can be to a storage vessel at the        olefin-derived petrochemical facility or directly to the        olefin-derived petrochemical formation reactor) through        interconnected pipes, optionally through one or more storage        vessels and valves or interlocks, and the r-olefin (e.g.        r-ethylene) feedstock is drawn through the interconnected        piping:        -   a. from the cracker facility while r-olefin (e.g.            r-ethylene) is being made or thereafter within the time for            the r-olefin (e.g. r-ethylene) to transport through the            piping to the olefin-derived petrochemical (e.g. AD or OG)            formation facility; or        -   b. from the one or more storage tanks at any time provided            that at least one of the storage tanks was fed with r-olefin            (e.g. r-ethylene), and continue for so long as the entire            volume of the one or more storage tanks is replaced with a            feed that does not contain r-olefin (e.g. r-ethylene); or    -   (ii) transporting olefin (e.g. ethylene) from a storage vessel,        dome, or facility, or in an isotainer via truck or rail or ship        or a means other than piping, that contains or has been fed with        r-olefin (e.g. r-ethylene) until such time as the entire volume        of the vessel, dome or facility has been replaced with an olefin        (e.g. ethylene) feed that does not contain r-olefin (e.g.        r-ethylene); or    -   (iii) the manufacturer of the olefin-derived petrochemical (e.g.        AD or OG) certifies, represents to its customers or the public,        or advertises that its olefin-derived petrochemical contains        recycle content or is obtained from feedstock containing or        obtained from recycle content, where such recycle content claim        is based in whole or in part on obtaining r-olefin (e.g.        ethylene feedstock associated with an allocation from ethylene        made from cracking r-pyoil or obtained from r-pygas); or    -   (iv) the manufacturer of the olefin-derived petrochemical (e.g.        AD or OG) has acquired:        -   a. an olefin (e.g. ethylene or propylene) volume made from            r-pyoil under a certification, representation, or as            advertised, or        -   b. has transferred credits or allocation with the supply of            olefin to the manufacturer of the olefin-derived            petrochemical (e.g. AD or OG) sufficient to allow the            manufacturer of the olefin-derived petrochemical (e.g. AD or            OG) to satisfy the certification requirements or to make its            representations or advertisements, or        -   c. an olefin that has an associated recycle content value            where such recycle content value was obtained, through one            or more intermediary independent entities, from r-pyoil or            cracking r-pyoil or an olefin obtained from cracking r-pyoil            or obtained from r-pygas.

As discussed above, the recycle content can be a pyrolysis recyclecontent that is directly or indirectly derived from the pyrolysis ofrecycled waste (e.g., from cracking r-pyoil or from r-pygas).

In one embodiment or in combination with any of the mentionedembodiments, the recycle content input or creation (recycle contentfeedstock or allotments) can be to or at a first Site, and recyclecontent values from said inputs are transferred to a second Site andapplied to one or more compositions made at a second Site. The recyclecontent values can be applied symmetrically or asymmetrically to thecompositions at the second Site. A recycle content value that isdirectly or indirectly “derived from cracking r-pyoil”, or a recyclecontent value that is “obtained from cracking r-pyoil” or originating incracking r-pyoil does not imply the timing of when the recycle contentvalue or allotment is taken, captured, deposited into a recycle contentinventory, or transferred. The timing of depositing the allotment orrecycle content value into a recycle content inventory, or realizing,recognizing, capturing, or transferring it, is flexible and can occur asearly as receipt of r-pyoil onto the site within a Family of Entities,possessing it, or bringing the r-pyoil into inventory by the entity orperson, or within the Family of Entities, owning or operating thecracker facility. Thus, an allotment or recycle content value on avolume of r-pyoil can be obtained, captured, deposited into aninventory, or transferred to a product without having yet fed thatvolume to cracker furnace and cracked. The allotment can also beobtained during feeding r-pyoil to a cracker, during cracking, or whenan r-composition is made. An allotment taken when r-pyoil is owned,possessed, or received and deposited into a recycle content inventory isan allotment that is associated with, obtained from, or originates fromcracking r-pyoil even though, at the time of taking or depositing theallotment, the r-pyoil has not yet been cracked, provided that ther-pyoil is at some future point in time cracked.

In one embodiment or in combination with any mentioned embodiments, theolefin-containing effluent manufacturer generates an allotment fromr-pyoil, and either:

-   -   a. applies the allotment to any PIA made directly or indirectly        (e.g. through a reaction scheme of several intermediates) from        cracking r-pyoil; or    -   b. applies the allotment to any PIA not made directly or        indirectly from cracking r-pyoil, such as would be the case        where the PIA is already made and stored in inventory or future        made PIA; or    -   c. deposited into an inventory from which is deducted any        allotment that is applied to PIA; and the deposited allotment        either is or is not associated with the particular allotment        applied to the PIA; or    -   d. is deposited into an inventory and stored for use at a later        time.

In one embodiment or in combination with any mentioned embodiments, onemay communicate recycle content information about the Recycle PIA to athird party where such recycle content information is based on orderived from at least a portion of the allocation or credit. The thirdparty may be a customer of the olefin-containing effluent manufactureror of the Recycle PIA manufacturer or may be any other person or entityor governmental organization other than the entity owning the either ofthem. The communication may electronic, by document, by advertisement,or any other means of communication.

In one embodiment or in combination with any mentioned embodiments,there is provided a system or package comprising:

-   -   a. Recycle PIA, and    -   b. an identifier such as a credit, label or certification        associated with said PIA, where the identifier is a        representation that the PIA has, or is sourced from, a recycle        content (which does not have to identify the source of the        recycle content or allotment);        provided that the Recycle PIA made thereby has an allotment, or        is made from a reactant, at least in part associated with        r-pyoil.

As used throughout, the step of deducting an allotment from a recyclecontent inventory does not require its application to a Recycle PIAproduct. The deduction also does not mean that the quantity disappearsor is removed from the inventory logs. A deduction can be an adjustmentof an entry, a withdrawal, an addition of an entry as a debit, or anyother algorithm that adjusts inputs and outputs based on an amountrecycle content associated with a product and one or a cumulative amountof allotments on deposit in the inventory. For example, a deduction canbe a simple step of a reducing/debit entry from one column and anaddition/credit to another column within the same program or books, oran algorithm that automates the deductions and entries/additions and/orapplications or designations to a product slate. The step of applying anallotment to a PIA where such allotment was deducted from inventory alsodoes not require the allotment to be applied physically to a Recycle PIAproduct or to any document issued in association with the Recycle PIAproduct sold. For example, a Recycle PIA manufacturer may ship RecyclePIA product to a customer and satisfy the “application” of the allotmentto the Recycle PIA product by electronically transferring a recyclecontent credit to the customer.

There is also provided a use for r-pyoil, the use including convertingr-pyoil in a gas cracker furnace to make an olefin-containing effluent.There is also provided a use for a r-pyoil that includes converting areactant in a synthetic process to make a PIA and applying at least aportion of an allotment to the PIA, where the allotment is associatedwith r-pyoil or has its origin in an inventory of allotments where atleast one deposit made into the inventory is associated with r-pyoil.

In one embodiment or in combination with any mentioned embodiments,there is provided a Recycle PIA that is obtained by any of the methodsdescribed above.

In an embodiment, the process for making Recycle PIA can be anintegrated process. One such example is a process to make Recycle PIAby:

-   -   a. cracking r-pyoil to make an olefin-containing effluent; and    -   b. separating compounds in said olefin-containing effluent to        obtain a separated compound; and    -   c. reacting any reactant in a synthetic process to make a PIA;    -   d. depositing an allotment into an inventory of allotments, said        allotment originating from r-pyoil; and    -   e. applying any allotment from said inventory to the PIA to        thereby obtain a Recycle PIA.

In one embodiment or in combination with any mentioned embodiments, onemay integrate two or more facilities and make Recycle PIA. Thefacilities to make Recycle PIA, or the olefin-containing effluent, canbe stand-alone facilities or facilities integrated to each other. Forexample, one may establish a system of producing and consuming areactant, as follows:

-   -   a. provide an olefin-containing effluent manufacturing facility        configured to produce a reactant;    -   b. provide a PIA manufacturing facility having a reactor        configured to accept a reactant from the olefin-containing        effluent manufacturing facility; and    -   c. a supply system providing fluid communication between these        two facilities and capable of supplying a reactant from the        olefin-containing effluent manufacturing facility to the PIA        manufacturing facility, wherein the olefin-containing effluent        manufacturing facility generates or participates in a process to        generate allotments and cracks r-pyoil, and:    -   (i) said allotments are applied to the reactants or to the PIA,        or    -   (ii) are deposited into an inventory of allotments, and        optionally an allotment    -   is withdrawn from the inventory and applied to the reactants or        to the PIA.

The Recycle PIA manufacturing facility can make Recycle PIA by acceptingany reactant from the olefin-containing effluent manufacturing facilityand applying a recycle content to Recycle PIA made with the reactant bydeducting allotments from its inventory and applying them to the PIA.

In one embodiment or in combination with any mentioned embodiments,there is also provided a system for producing Recycle PIA as follows:

-   -   a. provide an olefin-containing effluent manufacturing facility        configured to produce an output composition comprising an        olefin-containing effluent;    -   b. provide a reactant manufacturing facility configured to        accept a compound separated from the olefin-containing effluent        and making, through a reaction scheme one or more downstream        products of said compound to make an output composition        comprising a reactant;    -   c. provide a PIA manufacturing facility having a reactor        configured to accept a reactant and making an output composition        comprising PIA; and    -   d. a supply system providing fluid communication between at        least two of these facilities and capable of supplying the        output composition of one manufacturing facility to another one        or more of said manufacturing facilities.

The PIA manufacturing facility can make Recycle PIA. In this system, theolefin-containing effluent manufacturing facility can have its output influid communication with the reactant manufacturing facility which inturn can have its output in fluid communication with the PIAmanufacturing facility. Alternatively, the manufacturing facilities ofa) and b) alone can be in fluid communication, or only b) and c). In thelatter case, the PIA manufacturing facility can make Recycle PIA bydeducting allotments from it recycle content inventory and applying themto the PIA. The allotments obtained and stored in inventory can beobtained by any of the methods described above.

The fluid communication can be gaseous or liquid or both. The fluidcommunication need not be continuous and can be interrupted by storagetanks, valves, or other purification or treatment facilities, so long asthe fluid can be transported from the manufacturing facility to thesubsequent facility through an interconnecting pipe network and withoutthe use of truck, train, ship, or airplane. Further, the facilities mayshare the same site, or in other words, one site may contain two or moreof the facilities. Additionally, the facilities may also share storagetank sites, or storage tanks for ancillary chemicals, or may also shareutilities, steam or other heat sources, etc., yet also be considered asdiscrete facilities since their unit operations are separate. A facilitywill typically be bounded by a battery limit.

In one embodiment or in combination with any mentioned embodiments, theintegrated process includes at least two facilities co-located within 5,or within 3, or within 2, or within 1 mile of each other (measured as astraight line). In one embodiment or in combination with any mentionedembodiments, at least two facilities are owned by the same Family ofEntities.

There is also provided a circular manufacturing process comprising:

-   -   a. providing a r-pyoil, and    -   b. cracking the r-pyoil to produce an olefin-containing        effluent, and        -   (i) reacting a compound separated from said            olefin-containing effluent to make a Recycle PIA, or        -   (ii) associating a recycle content allotment, obtained from            said r-pyoil, to the PIA made from compounds separated from            a non-recycle olefin-containing effluent, to produce a            Recycle PIA; and    -   c. taking back at least a portion of any of said Recycle PIA or        any other articles, compounds, or polymer made from said Recycle        PIA, as a feedstock to make said r-pyoil.

In the above described process, an entirely circular or closed loopprocess is provided in which Recycle PIA can be recycled multiple times.

Examples of articles that are included in PIA are fibers, yams, tow,continuous filaments, staple fibers, rovings, fabrics, textiles, flake,film (e.g. polyolefin films), sheet, compounded sheet, plasticcontainers, and consumer articles.

In one embodiment or in combination with any mentioned embodiments, theRecycle PIA is a polymer or article of the same family or classificationof polymers or articles used to make r-pyoil.

The terms “recycled waste,” “waste stream,” and “recycled waste stream”are used interchangeably to mean any type of waste or waste-containingstream that is reused in a production process, rather than beingpermanently disposed of (e.g., in a landfill or incinerator). Therecycled waste stream is a flow or accumulation of recycled waste fromindustrial and consumer sources that is at least in part recovered.

A recycled waste stream includes materials, products, and articles(collectively “material(s)” when used alone). Recycled waste materialscan be solid or liquid. Examples of a solid recycled waste streaminclude plastics, rubber (including tires), textiles, wood, biowaste,modified celluloses, wet laid products, and any other material capableof being pyrolyzed. Examples of liquid waste streams include industrialsludge, oils (including those derived from plants and petroleum),recovered lube oil, or vegetable oil or animal oil, and any otherchemical streams from industrial plants.

In one embodiment or in combination with any of the mentionedembodiments, the recycled waste stream that is pyrolyzed includes astream containing at least in part post-industrial, or post-consumer, orboth a post-industrial and post-consumer materials. In one embodiment orin combination with any of the mentioned embodiments, a post-consumermaterial is one that has been used at least once for its intendedapplication for any duration of time regardless of wear, or has beensold to an end use customer, or which is discarded into a recycle bin byany person or entity other than a manufacturer or business engaged inthe manufacture or sale of the material.

In one embodiment or in combination with any of the mentionedembodiments, a post-industrial material is one which has been createdand has not been used for its intended application, or has not been soldto the end use customer, or discarded by a manufacturer or any otherentity engaged in the sale of the material. Examples of post-industrialmaterials include rework, regrind, scrap, trim, out of specificationmaterials, and finished materials transferred from a manufacturer to anydownstream customer (e.g. manufacturer to wholesaler to distributor) butnot yet used or sold to the end use customer.

The form of the recycled waste stream, which can be fed to a pyrolysisunit, is not limited, and can include any of the forms of articles,products, materials, or portions thereof. A portion of an article cantake the form of sheets, extruded shapes, moldings, films, laminates,foam pieces, chips, flakes, particles, fibers, agglomerates, briquettes,powder, shredded pieces, long strips, or randomly shaped pieces having awide variety of shapes, or any other form other than the original formof the article and adapted to feed a pyrolysis unit.

In one embodiment or in combination with any of the mentionedembodiments, the recycled waste material is size reduced. Size reductioncan occur through any means, including chopping, shredding, harrowing,confrication, pulverizing, cutting a feedstock, molding, compression, ordissolution in a solvent.

Recycled waste plastics can be isolated as one type of polymer stream ormay be a stream of mixed recycled waste plastics. The plastics can beany organic synthetic polymer that is solid at 25° C. at 1 atm. Theplastics can be thermosetting, thermoplastic, or elastomeric plastics.Examples of plastics include high density polyethylene and copolymersthereof, low density polyethylene and copolymers thereof, polypropyleneand copolymers thereof, other polyolefins, polystyrene, polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyesters includingpolyethylene terephthalate, copolyesters and terephthalate copolyesters(e.g. containing residues of TMCD, CHDM, propylene glycol, or NPGmonomers), polyethylene terephthalate, polyamides, poly(methylmethacrylate), polytetrafluoroethylene, acrylobutadienestyrene (ABS),polyurethanes, cellulosics and derivates thereof such as celluloseacetate, cellulose diacetate, cellulose triacetate, cellulosepropionate, cellulose butyrate; regenerated cellulosics such as viscoseand rayons, epoxy, polyamides, phenolic resins, polyacetal,polycarbonates, polyphenylene-based alloys, polypropylene and copolymersthereof, polystyrene, styrenic compounds, vinyl based compounds, styreneacrylonitrile, thermoplastic elastomers, and urea based polymers andmelamine containing polymers.

Suitable recycled waste plastics also include any of those having aresin ID code numbered 1-7 within the chasing arrow triangle establishedby the SPI. In one embodiment or in combination with any of thementioned embodiments, the r-pyoil is made from a recycled waste streamat least a portion of which contains plastics that are not generallyrecycled. These would include plastics having numbers 3 (polyvinylchloride), 5 (polypropylene), 6 (polystyrene), and 7 (other). In oneembodiment or in combination with any of the mentioned embodiments, therecycled waste stream that is pyrolyzed contains less than 10 weightpercent, or not more than 5 weight percent, or not more than 3 weightpercent, or not more than 2 weight percent, or not more than 1 weightpercent, or not more than 0.5 weight percent, or not more than 0.2weight percent, or not more than 0.1 weight percent, or not more and0.05 weight percent plastics with a number 3 designation (polyvinylchloride), or optionally plastics with a number 3 and 6 designation, oroptionally with a number 3, 6 and 7 designation.

Examples of recycled rubber include natural and synthetic rubber. Theform of the rubber is not limited, and includes tires.

Examples of recycled waste wood include soft and hard woods, chipped,pulped, or as finished articles. The source of much recycled waste woodis industrial, construction, or demolition.

Examples of recycled biorecycled waste includes household biorecycledwaste (e.g. food), green or garden biorecycled waste, and biorecycledwaste from the industrial food processing industry.

Examples of recycled textiles includes natural and/or synthetic fibers,rovings, yams, nonwoven webs, cloth, fabrics and products made from orcontaining any of the aforementioned items. Textiles can be woven,knitted, knotted, stitched, tufted, pressing of fibers together such aswould be done in a felting operation, embroidered, laced, crocheted,braided, or nonwoven webs and materials. Textiles include fabrics, andfibers separated from a textile or other product containing fibers,scrap or off spec fibers or yarns or fabrics, or any other source ofloose fibers and yams. A textile also includes staple fibers, continuousfibers, threads, tow bands, twisted and/or spun yams, grey fabrics madefrom yams, finished fabrics produced by wet processing gray fabrics, andgarments made from the finished fabrics or any other fabrics. Textilesinclude apparels, interior furnishings, and industrial types oftextiles.

Examples of recycled textiles in the apparel category (things humanswear or made for the body) include sports coats, suits, trousers andcasual or work pants, shirts, socks, sportswear, dresses, intimateapparel, outerwear such as rain jackets, cold temperature jackets andcoats, sweaters, protective clothing, uniforms, and accessories such asscarves, hats, and gloves. Examples of textiles in the interiorfurnishing category include furniture upholstery and slipcovers, carpetsand rugs, curtains, bedding such as sheets, pillow covers, duvets,comforters, mattress covers; linens, table cloths, towels, washcloths,and blankets. Examples of industrial textiles include transportation(auto, airplanes, trains, buses) seats, floor mats, trunk liners, andheadliners; outdoor furniture and cushions, tents, backpacks, luggage,ropes, conveyor belts, calendar roll felts, polishing cloths, rags, soilerosion fabrics and geotextiles, agricultural mats and screens, personalprotective equipment, bullet proof vests, medical bandages, sutures,tapes, and the like.

The recycled nonwoven webs can also be dry laid nonwoven webs. Examplesof suitable articles that may be formed from dry laid nonwoven webs asdescribed herein can include those for personal, consumer, industrial,food service, medical, and other types of end uses. Specific examplescan include, but are not limited to, baby wipes, flushable wipes,disposable diapers, training pants, feminine hygiene products such assanitary napkins and tampons, adult incontinence pads, underwear, orbriefs, and pet training pads. Other examples include a variety ofdifferent dry or wet wipes, including those for consumer (such aspersonal care or household) and industrial (such as food service, healthcare, or specialty) use. Nonwoven webs can also be used as padding forpillows, mattresses, and upholstery, batting for quilts and comforters.In the medical and industrial fields, nonwoven webs of the presentinvention may be used for medical and industrial face masks, protectiveclothing, caps, and shoe covers, disposable sheets, surgical gowns,drapes, bandages, and medical dressings. Additionally, nonwoven webs maybe used for environmental fabrics such as geotextiles and tarps, oil andchemical absorbent pads, as well as building materials such as acousticor thermal insulation, tents, lumber and soil covers and sheeting.Nonwoven webs may also be used for other consumer end use applications,such as for, carpet backing, packaging for consumer, industrial, andagricultural goods, thermal or acoustic insulation, and in various typesof apparel. The dry laid nonwoven webs may also be used for a variety offiltration applications, including transportation (e.g., automotive oraeronautical), commercial, residential, industrial, or other specialtyapplications. Examples can include filter elements for consumer orindustrial air or liquid filters (e.g., gasoline, oil, water), includingnanofiber webs used for microfiltration, as well as end uses like teabags, coffee filters, and dryer sheets. Further, nonwoven webs may beused to form a variety of components for use in automobiles, including,but not limited to, brake pads, trunk liners, carpet tufting, and underpadding.

The recycled textiles can include single type or multiple type ofnatural fibers and/or single type or multiple type of synthetic fibers.Examples of textile fiber combinations include all natural, allsynthetic, two or more type of natural fibers, two or more types ofsynthetic fibers, one type of natural fiber and one type of syntheticfiber, one type of natural fibers and two or more types of syntheticfibers, two or more types of natural fibers and one type of syntheticfibers, and two or more types of natural fibers and two or more types ofsynthetic fibers.

Examples of recycled wet laid products include cardboard, office paper,newsprint and magazine, printing and writing paper, sanitary,tissue/toweling, packaging/container board, specialty papers, apparel,bleached board, corrugated medium, wet laid molded products, unbleachedKraft, decorative laminates, security paper and currency, grand scalegraphics, specialty products, and food and drink products.

Examples of modified cellulose include cellulose acetate, cellulosediacetate, cellulose triacetate, regenerated cellulose such a viscose,rayon, and Lyocel™ products, in any form, such as tow bands, staplefibers, continuous fibers, films, sheets, molded or stamped products,and contained in or on any article such as cigarette filter rods,ophthalmic products, screwdrivers handles, optical films, and coatings.

Examples of recycled vegetable oil or animal oil include the oilsrecovered from animal processing facilities and recycled waste fromrestaurants.

The source for obtaining recycled post-consumer or post-industrialrecycled waste is not limited, and can include recycled waste present inand/or separated from municipal solid recycled waste streams (“MSW”).For example, an MSW stream can be processed and sorted to severaldiscrete components, including textiles, fibers, papers, wood, glass,metals, etc. Other sources of textiles include those obtained bycollection agencies, or by or for or on behalf of textile brand ownersor consortiums or organizations, or from brokers, or from postindustrialsources such as scrap from mills or commercial production facilities,unsold fabrics from wholesalers or dealers, from mechanical and/orchemical sorting or separation facilities, from landfills, or strandedon docks or ships.

In one embodiment or in combination with any of the mentionedembodiments, the feed to the pyrolysis unit can comprise at least 30, orat least 35, or at least 40, or at least 45, or at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, or at least99, in each case weight percent of at least one, or at least two, or atleast three, or at least four, or at least five, or at least sixdifferent kinds of recycled waste. Reference to a “kind” is determinedby resin ID code 1-7. In one embodiment or in combination with any ofthe mentioned embodiments, the feed to the pyrolysis unit contains lessthan 25, or not more than 20, or not more than 15, or not more than 10,or not more than 5, or not more than 1, in each case weight percent ofpolyvinyl chloride and/or polyethylene terephthalate. In one embodimentor in combination with any of the mentioned embodiments, the recycledwaste stream contains at least one, two, or three kinds of plasticizedplastics.

FIG. 2 depicts an exemplary pyrolysis system 110 that may be employed toat least partially convert one or more recycled waste, particularlyrecycled plastic waste, into various useful pyrolysis-derived products.It should be understood that the pyrolysis system shown in FIG. 2 isjust one example of a system within which the present disclosure can beembodied. The present disclosure may find application in a wide varietyof other systems where it is desirable to efficiently and effectivelypyrolyze recycled waste, particularly recycled plastic waste, intovarious desirable end products. The exemplary pyrolysis systemillustrated in FIG. 2 will now be described in greater detail.

As shown in FIG. 2, the pyrolysis system 110 may include a waste plasticsource 112 for supplying one or more waste plastics to the system 110.The plastic source 112 can be, for example, a hopper, storage bin,railcar, over-the-road trailer, or any other device that may hold orstore waste plastics. In an embodiment or in combination with any of theembodiments mentioned herein, the waste plastics supplied by the plasticsource 112 can be in the form of solid particles, such as chips, flakes,or a powder. Although not depicted in FIG. 2, the pyrolysis system 110may also comprise additional sources of other types of recycled wastesthat may be utilized to provide other feed types to the system 110.

In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastics can include one or more post-consumer wasteplastic such as, for example, high density polyethylene, low densitypolyethylene, polypropylene, other polyolefins, polystyrene, polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyethyleneterephthalate, polyamides, poly(methyl methacrylate),polytetrafluoroethylene, or combinations thereof. In an embodiment or incombination with any of the embodiments mentioned herein, the wasteplastics may include high density polyethylene, low densitypolyethylene, polypropylene, or combinations thereof. As used herein,“post-consumer” refers to non-virgin plastics that have been previouslyintroduced into the consumer market.

In an embodiment or in combination with any of the embodiments mentionedherein, a waste plastic-containing feed may be supplied from the plasticsource 112. In an embodiment or in combination with any of theembodiments mentioned herein, the waste plastic-containing feed cancomprise, consist essentially of, or consist of high densitypolyethylene, low density polyethylene, polypropylene, otherpolyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidenechloride (PVDC), polyethylene terephthalate, polyamides, poly(methylmethacrylate), polytetrafluoroethylene, or combinations thereof.

In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastic-containing feed can comprise at least 30, orat least 35, or at least 40, or at least 45, or at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, or at least99, in each case weight percent of at least one, two, three, or fourdifferent kinds of waste plastic. In an embodiment or in combinationwith any of the embodiments mentioned herein, the plastic waste maycomprise not more than 25, or not more than 20, or not more than 15, ornot more than 10, or not more than 5, or not more than 1, in each caseweight percent of polyvinyl chloride and/or polyethylene terephthalate.In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastic-containing feed can comprise at least one,two, or three kinds of plasticized plastics. Reference to a “kind” isdetermined by resin ID code 1-7.

As depicted in FIG. 2, the solid waste plastic feed from the plasticsource 112 can be supplied to a feedstock pretreatment unit 114. Whilein the feedstock pretreatment unit 114, the introduced waste plasticsmay undergo a number of pretreatments to facilitate the subsequentpyrolysis reaction. Such pretreatments may include, for example,washing, mechanical agitation, flotation, size reduction or anycombination thereof. In an embodiment or in combination with any of theembodiments mentioned herein, the introduced plastic waste may besubjected to mechanical agitation or subjected to size reductionoperations to reduce the particle size of the plastic waste. Suchmechanical agitation can be supplied by any mixing, shearing, orgrinding device known in the art which may reduce the average particlesize of the introduced plastics by at least 10, or at least 25, or atleast 50, or at least 75, in each case percent.

Next, the pretreated plastic feed can be introduced into a plastic feedsystem 116. The plastic feed system 116 may be configured to introducethe plastic feed into the pyrolysis reactor 118. The plastic feed system116 can comprise any system known in the art that is capable of feedingthe solid plastic feed into the pyrolysis reactor 118. In an embodimentor in combination with any of the embodiments mentioned herein, theplastic feed system 116 can comprise a screw feeder, a hopper, apneumatic conveyance system, a mechanic metal train or chain, orcombinations thereof.

While in the pyrolysis reactor 118, at least a portion of the plasticfeed may be subjected to a pyrolysis reaction that produces a pyrolysiseffluent comprising a pyrolysis oil (e.g., r-pyoil) and a pyrolysis gas(e.g., r-pyrolysis gas). The pyrolysis reactor 118 can be, for example,an extruder, a tubular reactor, a tank, a stirred tank reactor, a riserreactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, avacuum reactor, a microwave reactor, an ultrasonic or supersonicreactor, or an autoclave, a film reactor, or a combination of thesereactors.

Generally, pyrolysis is a process that involves the chemical and thermaldecomposition of the introduced feed. Although all pyrolysis processesmay be generally characterized by a reaction environment that issubstantially free of oxygen, pyrolysis processes may be furtherdefined, for example, by the pyrolysis reaction temperature within thereactor, the residence time in the pyrolysis reactor, the reactor type,the pressure within the pyrolysis reactor, and the presence or absenceof pyrolysis catalysts.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction can involve heating and converting theplastic feed in an atmosphere that is substantially free of oxygen or inan atmosphere that contains less oxygen relative to ambient air. In anembodiment or in combination with any of the embodiments mentionedherein, the atmosphere within the pyrolysis reactor 118 may comprise notmore than 5, or not more than 4, or not more than 3, or not more than 2,or not more than 1, or not more than 0.5, in each case weight percent ofoxygen gas.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis process may be carried out in the presence of aninert gas, such as nitrogen, carbon dioxide, and/or steam. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis process can be carried outin the presence of a reducing gas, such as hydrogen and/or carbonmonoxide.

In an embodiment or in combination with any of the embodiments mentionedherein, the temperature in the pyrolysis reactor 118 can be adjusted toas to facilitate the production of certain end products. In anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis temperature in the pyrolysis reactor 118 can be atleast 325° C., or at least 350° C., or at least 375° C., or at least400° C., or at least 425° C., or at least 450° C., or at least 475° C.,or at least 500° C., or at least 525° C., or at least 550° C., or atleast 575° C., or at least 600° C., or at least 625° C., or at least650° C., or at least 675° C., or at least 700° C., or at least 725° C.,or at least 750° C., or at least 775° C., or at least 800° C.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis temperature inthe pyrolysis reactor 118 can be not more than 1,100° C., or not morethan 1,050° C., or not more than 1,000° C., or not more than 950° C., ornot more than 900° C., or not more than 850° C., or not more than 800°C., or not more than 750° C., or not more than 700° C., or not more than650° C., or not more than 600° C., or not more than 550° C., or not morethan 525° C., or not more than 500° C., or not more than 475° C., or notmore than 450° C., or not more than 425° C., or not more than 400° C. Inan embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis temperature in the pyrolysis reactor 118 can rangefrom 325 to 1,100° C., 350 to 900° C., 350 to 700° C., 350 to 550° C.,350 to 475° C., 500 to 1,100° C., 600 to 1,100° C., or 650 to 1,000° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the residence times of the pyrolysis reaction can be at least 1,or at least 2, or at least 3, or at least 4, in each case seconds, or atleast 10, or at least 20, or at least 30, or at least 45, or at least60, or at least 75, or at least 90, in each case minutes. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the residence times of the pyrolysisreaction can be not more than 6 hours, or not more than 5, or not morethan 4, or not more than 3, or not more than 2, or not more than 1, ornot more than 0.5, in each case hours. In an embodiment or incombination with any of the embodiments mentioned herein, the residencetimes of the pyrolysis reaction can range from 30 minutes to 4 hours, or30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

In an embodiment or in combination with any of the embodiments mentionedherein, the pressure within the pyrolysis reactor 118 can be maintainedat a pressure of at least 0.1, or at least 0.2, or at least 0.3, in eachcase bar and/or not more than 60, or not more than 50, or not more than40, or not more than 30, or not more than 20, or not more than 10, ornot more than 8, or not more than 5, or not more than 2, or not morethan 1.5, or not more than 1.1, in each case bar. In an embodiment or incombination with any of the embodiments mentioned herein, the pressurewithin the pyrolysis reactor 18 can be maintained at about atmosphericpressure or within the range of 0.1 to 100 bar, or 0.1 to 60 bar, or 0.1to 30 bar, or 0.1 to 10 bar, or 1.5 bar, 0.2 to 1.5 bar, or 0.3 to 1.1bar.

In an embodiment or in combination with any of the embodiments mentionedherein, a pyrolysis catalyst may be introduced into the plastic feedprior to introduction into the pyrolysis reactor 118 and/or introduceddirectly into the pyrolysis reactor 118 to produce an r-catalytic pyoil,or an r-pyoil made by a catalytic pyrolysis process. In an embodiment orin combination with any embodiment mentioned herein or in combinationwith any of the embodiments mentioned herein, the catalyst can comprise:(i) a solid acid, such as a zeolite (e.g., ZSM-5, Mordenite, Beta,Ferrierite, and/or zeolite-Y); (ii) a super acid, such as sulfonated,phosphated, or fluorinated forms of zirconia, titania, alumina,silica-alumina, and/or clays; (iii) a solid base, such as metal oxides,mixed metal oxides, metal hydroxides, and/or metal carbonates,particularly those of alkali metals, alkaline earth metals, transitionmetals, and/or rare earth metals; (iv) hydrotalcite and other clays; (v)a metal hydride, particularly those of alkali metals, alkaline earthmetals, transition metals, and/or rare earth metals; (vi) an aluminaand/or a silica-alumina; (vii) a homogeneous catalyst, such as a Lewisacid, a metal tetrachloroaluminate, or an organic ionic liquid; (viii)activated carbon; or (ix) combinations thereof.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction in the pyrolysis reactor 118 occurs inthe substantial absence of a catalyst, particularly the above-referencedcatalysts. In such embodiments, a non-catalytic, heat-retaining inertadditive may still be introduced into the pyrolysis reactor 118, such assand, in order to facilitate the heat transfer within the reactor 118.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction in the pyrolysis reactor 118 may occur inthe substantial absence of a pyrolysis catalyst, at a temperature in therange of 350 to 550° C., at a pressure ranging from 0.1 to 60 bar, andat a residence time of 0.2 seconds to 4 hours, or 0.5 hours to 3 hours.

Referring again to FIG. 2, the pyrolysis effluent 120 exiting thepyrolysis reactor 118 generally comprises pyrolysis gas, pyrolysisvapors, and residual solids. As used herein, the vapors produced duringthe pyrolysis reaction may interchangeably be referred to as a“pyrolysis oil,” which refers to the vapors when condensed into theirliquid state. In an embodiment or in combination with any of theembodiments mentioned herein, the solids in the pyrolysis effluent 20may comprise particles of char, ash, unconverted plastic solids, otherunconverted solids from the feedstock, and/or spent catalyst (if acatalyst is utilized).

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise at least 20, or at least25, or at least 30, or at least 40, or at least 45, or at least 50, orat least 55, or at least 60, or at least 65, or at least 70, or at least75, or at least or at least 80, in each case weight percent of thepyrolysis vapors, which may be subsequently condensed into the resultingpyrolysis oil (e.g., r-pyoil). Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise not more than 99, or notmore than 95, or not more than 90, or not more than 85, or not more than80, or not more than 75, or not more than 70, or not more than 65, ornot more than 60, or not more than 55, or not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,in each case weight percent of the pyrolysis vapors. In an embodiment orin combination with any of the embodiments mentioned herein, thepyrolysis effluent 120 may comprise in the range of 20 to 99 weightpercent, 40 to 90 weight percent, or 55 to 90 weight percent of thepyrolysis vapors.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise at least 1, or at least5, or at least 6, or at least 7, or at least 8, or at least 9, or atleast 10, or at least 11, or at least 12, in each case weight percent ofthe pyrolysis gas (e.g., r-pyrolysis gas). As used herein, a “pyrolysisgas” refers to a composition that is produced via pyrolysis and is a gasat standard temperature and pressure (STP). Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis effluent 20 may comprise notmore than 90, or not more than 85, or not more than 80, or not more than75, or not more than 70, or not more than 65, or not more than 60, ornot more than 55, or not more than 50, or not more than 45, or not morethan 40, or not more than 35, or not more than 30, or not more than 25,or not more than 20, or not more than 15, in each case weight percent ofthe pyrolysis gas. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis effluent 120 may comprise 1to 90 weight percent, or 5 to 60 weight percent, or 10 to 60 weightpercent, or 10 to 30 weight percent, or 5 to 30 weight percent of thepyrolysis gas.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise not more than 15, or notmore than 10, or not more than 9, or not more than 8, or not more than7, or not more than 6, or not more than 5, or not more than 4 or notmore than 3, in each case weight percent of the residual solids.

In one embodiment or in combination of any mentioned embodiments, thereis provided a cracker feed stock composition containing r-pyoil, and ther-pyoil composition contains recycle content catalytic pyrolysis oil(r-catalytic pyoil) and a recycle content thermal pyrolysis oil(r-thermal pyoil). An r-thermal pyoil is pyoil made without the additionof a pyrolysis catalyst. The cracker feedstock can include at least 5,10, 15, or 20 weight percent r-catalytic pyoil, optionally that has beenhydrotreated. The r-pyoil containing r-thermal pyoil and r-catalyticpyoil can be cracked according to any of the processes described hereinto provide an olefin-containing effluent stream. The r-catalytic pyoilcan be blended with r-thermal pyoil to form a blended stream cracked inthe cracker unit. Optionally, the blended stream can contain not morethan 10, 5, 3, 2, 1 weight percent of r-catalytic pyoil that has notbeen hydrotreated.

In one embodiment or in combination with any mentioned embodiment, ther-pyoil does not contain r-catalytic pyoil.

As depicted in FIG. 2, the conversion effluent 120 from the pyrolysisreactor 118 can be introduced into a solids separator 122. The solidsseparator 122 can be any conventional device capable of separatingsolids from gas and vapors such as, for example, a cyclone separator ora gas filter or combination thereof. In an embodiment or in combinationwith any of the embodiments mentioned herein, the solids separator 122removes a substantial portion of the solids from the conversion effluent120. In an embodiment or in combination with any of the embodimentsmentioned herein, at least a portion of the solid particles 24 recoveredin the solids separator 122 may be introduced into an optionalregenerator 126 for regeneration, generally by combustion. Afterregeneration, at least a portion of the hot regenerated solids 128 canbe introduced directly into the pyrolysis reactor 118. In an embodimentor in combination with any of the embodiments mentioned herein, at leasta portion of the solid particles 124 recovered in the solids separator122 may be directly introduced back into the pyrolysis reactor 118,especially if the solid particles 124 contain a notable amount ofunconverted plastic waste. Solids can be removed from the regenerator126 through line 145 and discharged out of the system.

Turning back to FIG. 2, the remaining gas and vapor conversion products130 from the solids separator 122 may be introduced into a fractionator132. In the fractionator 132, at least a portion of the pyrolysis oilvapors may be separated from the pyrolysis gas to thereby form apyrolysis gas product stream 134 and a pyrolysis oil vapor stream 136.Suitable systems to be used as the fractionator 132 may include, forexample, a distillation column, a membrane separation unit, a quenchtower, a condenser, or any other known separation unit known in the art.In an embodiment or in combination with any of the embodiments mentionedherein, any residual solids 146 accrued in the fractionator 132 may beintroduced in the optional regenerator 126 for additional processing.

In an embodiment or in combination with any of the embodiments mentionedherein, at least a portion of the pyrolysis oil vapor stream 136 may beintroduced into a quench unit 138 in order to at least partially quenchthe pyrolysis vapors into their liquid form (i.e., the pyrolysis oil).The quench unit 138 may comprise any suitable quench system known in theart, such as a quench tower. The resulting liquid pyrolysis oil stream140 may be removed from the system 110 and utilized in the otherdownstream applications described herein. In an embodiment or incombination with any of the embodiments mentioned herein, the liquidpyrolysis oil stream 140 may not be subjected to any additionaltreatments, such as hydrotreatment and/or hydrogenation, prior to beingutilized in any of the downstream applications described herein.

In an embodiment or in combination with any embodiment mentioned herein,at least a portion of the pyrolysis oil vapor stream 136 may beintroduced into a hydroprocessing unit 142 for further refinement. Thehydroprocessing unit 142 may comprise a hydrocracker, a catalyticcracker operating with a hydrogen feed stream, a hydrotreatment unit,and/or a hydrogenation unit. While in the hydroprocessing unit 142, thepyrolysis oil vapor stream 136 may be treated with hydrogen and/or otherreducing gases to further saturate the hydrocarbons in the pyrolysis oiland remove undesirable byproducts from the pyrolysis oil. The resultinghydroprocessed pyrolysis oil vapor stream 144 may be removed andintroduced into the quench unit 138. Alternatively, the pyrolysis oilvapor may be cooled, liquified, and then treated with hydrogen and/orother reducing gases to further saturate the hydrocarbons in thepyrolysis oil. In this case, the hydrogenation or hydrotreating isperformed in a liquid phase pyrolysis oil. No quench step is required inthis embodiment post-hydrogenation or post-hydrotreating.

The pyrolysis system 110 described herein may produce a pyrolysis oil(e.g., r-pyoil) and pyrolysis gases (e.g., r-pyrolysis gas) that may bedirectly used in various downstream applications based on theirdesirable formulations. The various characteristics and properties ofthe pyrolysis oils and pyrolysis gases are described below. It should benoted that, while all of the following characteristics and propertiesmay be listed separately, it is envisioned that each of the followingcharacteristics and/or properties of the pyrolysis oils or pyrolysisgases are not mutually exclusive and may be combined and present in anycombination.

The pyrolysis oil may predominantly comprise hydrocarbons having from 4to 30 carbon atoms per molecule (e.g., C4 to C30 hydrocarbons). As usedherein, the term “Cx” or “Cx hydrocarbon,” refers to a hydrocarboncompound including x total carbons per molecule, and encompasses allolefins, paraffins, aromatics, and isomers having that number of carbonatoms. For example, each of normal, iso, and tert butane and butene andbutadiene molecules would fall under the general description “C4.”

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil fed to the cracking furnace may have a C4-C30hydrocarbon content of at least 55, or at least 60, or at least 65, orat least 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, in each case weight percent based on the weight ofthe pyrolysis oil.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil fed to the furnace can predominantly compriseC5-C25, C5-C22, or C5-C20hydrocarbons, or may comprise at least about55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, in eachcase weight percent of C5-C25, C5-C22, or C5-C20hydrocarbons, based onthe weight of the pyrolysis oil.

The gas furnace can tolerate a wide variety of hydrocarbon numbers inthe pyrolysis oil feedstock, thereby avoiding the necessity forsubjecting a pyrolysis oil feedstock to separation techniques to delivera smaller or lighter hydrocarbon cut to the cracker furnace. In oneembodiment or in any of the mentioned embodiments, the pyrolysis oilafter delivery from a pyrolysis manufacturer is not subjected aseparation process for separating a heavy hydrocarbon cut from a lighterhydrocarbon cut, relative to each other, prior to feeding the pyrolysisoil to a cracker furnace. The feed of pyrolysis oil to a gas furnaceallows one to employ a pyrolysis oil that contains heavy tail ends orhigher carbon numbers at or above 12. In one embodiment or in any of thementioned embodiments, the pyrolysis oil fed to a cracker furnace is aC5 to C25 hydrocarbon stream containing at least 1 wt. %, 3 wt. %, or atleast 5 wt. %, or at least 8 wt. %, or at least 10 wt. %, or at least 12wt. %, or at least 15 wt. %, or at least 18 wt. %, or at least 20 wt. %,or at least 25 wt. % or at least 30 wt. %, or at least 35 wt. %, or atleast 40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least55 wt. %, or at least 60 wt. % hydrocarbons within a range from C12 toC25, inclusive, or within a range of C14 to C25, inclusive, or within arange of C16 to C25, inclusive.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a C6 to C12 hydrocarbon content of atleast 10, or at least 15, or at least 20, or at least 25, or at least30, or at least 35, or at least 40, or at least 45, or at least 50, orat least 55, in each case weight percent, based on the weight of thepyrolysis oil. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have a C6-C12 hydrocarbon content of not more than 98.5, notmore than 95, or not more than 90, or not more than 85, or not more than80, or not more than 75, or not more than 70, or not more than 65, ornot more than 60, in each case weight percent. In an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have a C6-C12 hydrocarbon content in the range of 10 to 95weight percent, 20 to 80 weight percent, or 35 to 80 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a C13 to C23 hydrocarbon content ofat least 1, or at least 5, or at least 10, or at least 15, or at least20, or at least 25, or at least 30, in each case weight percent.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may have aC13 to C23 hydrocarbon content of not more than 80, or not more than 75,or not more than 70, or not more than 65, or not more than 60, or notmore than 55, or not more than 50, or not more than 45, or not more than40, in each case weight percent. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may have aC13 to C23 hydrocarbon content in the range of 1 to 80 weight percent, 5to 65 weight percent, or 10 to 60 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyrolysis oil, or r-pyoil fed to a cracker furnace, orr-pyoil fed to a cracker furnace that, prior to feeding-pyoil, accepts apredominately C2-C4 feedstock (and the mention of r-pyoil or pyrolysisoil throughout includes any of these embodiments), may have a C24+hydrocarbon content of at least 1, or at least 2, or at least 3, or atleast 4, or at least 5, in each case weight percent. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a C24+hydrocarbon content of not more than 15, or not more than 10, or notmore than 9, or not more than 8, or not more than 7, or not more than 6,in each case weight percent. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis oil may have a C24+hydrocarbon content in the range of 1 to 15 weight percent, 3 to 15weight percent, 2 to 5 weight percent, or 5 to 10 weight percent.

The pyrolysis oil may also include various amounts of olefins,aromatics, and other compounds. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil includes atleast 1, or at least 2, or at least 5, or at least 10, or at least 15,or at least 20, in each case weight percent olefins and/or aromatics.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may includenot more than 50, or not more than 45, or not more than 40, or not morethan 35, or not more than 30, or not more than 25, or not more than 20,or not more than 15, or not more than 10, or not more than 5, or notmore than 2, or not more than 1, in each case weight percent olefinsand/or aromatics.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an aromatic content of not more than25, or not more than 20, or not more than 15, or not more than 14, ornot more than 13, or not more than 12, or not more than 11, or not morethan 10, or not more than 9, or not more than 8, or not more than 7, ornot more than 6, or not more than 5, or not more than 4, or not morethan 3, or not more than 2, or not more than 1, in each case weightpercent. In one embodiment or in combination with any mentionedembodiments, the pyrolysis oil has an aromatic content that is nothigher than 15, or not more than 10, or not more than 8, or not morethan 6, in each case weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of at least 1, orat least 2, or at least 3, or at least 4, or at least 5, or at least 6,or at least 7, or at least 8, or at least 9, or at least 10, or at least11, or at least 12, or at least 13, or at least 14, or at least 15, ineach case weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of not more than50, or not more than 45, or not more than 40, or not more than 35, ornot more than 30, or not more than 25, or not more than 20, or not morethan 10, or not more than 5, or not more than 2, or not more than 1, ornot more than 0.5, or no detectable amount, in each case weight percent.In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of not more than5, or not more than 2, or not more than 1 wt. %, or no detectableamount, or naphthenes. Alternatively, the pyrolysis oil may contain inthe range of 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45weight percent naphthenes, especially if the r-pyoil was subjected to ahydrotreating process.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content of at least 25, orat least 30, or at least 35, or at least 40, or at least 45, or at least50, in each case weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content of not more than90, or not more than 85, or not more than 80, or not more than 75, ornot more than 70, or not more than 65, or not more than 60, or not morethan 55, in each case weight percent. In an embodiment or in combinationwith any of the embodiments mentioned herein, the pyrolysis oil may havea paraffin content in the range of 25 to 90 weight percent, 35 to 90weight percent, or 40 to 80, or 40-70, or 40-65 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an n-paraffin content of at least 5,or at least 10, or at least 15, or at least 25, or at least 30, or atleast 35, or at least 40, or at least 45, or at least 50, in each caseweight percent. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have an n-paraffin content of not more than 90, or not more than85, or not more than 80, or not more than 75, or not more than 70, ornot more than 65, or not more than 60, or not more than 55, in each caseweight percent. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have an n-paraffincontent in the range of 25 to 90 weight percent, 35 to 90 weightpercent, or 40-70, or 40-65, or 50 to 80 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin to olefin weight ratio ofat least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1,or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least0.9:1, or at least 1:1. Additionally, or alternatively, in an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil may have a paraffin to olefin weight ratio not more than3:1, or not more than 2.5:1, or not more than 2:1, or not more than1.5:1, or not more than 1.4:1, or not more than 1.3:1. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil may have a paraffin to olefin weight ratio in the range of0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an n-paraffin to i-paraffin weightratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or atleast 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or atleast 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or atleast 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or atleast 20:1. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have an n-paraffin to i-paraffin weight ratio of not more than100:1, 7 or not more than 5:1, or not more than 50:1, or not more than40:1, or not more than 30:1. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis oil may have ann-paraffin to i-paraffin weight ratio in the range of 1:1 to 100:1, 4:1to 100:1, or 15:1 to 100:1.

It should be noted that all of the above-referenced hydrocarbon weightpercentages may be determined using gas chromatography-mass spectrometry(GC-MS).

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may exhibit a density at 15° C. of at least0.6 g/cm3, or at least 0.65 g/cm3, or at least 0.7 g/cm3. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may exhibit a density at15° C. of not more than 1 g/cm3, or not more than 0.95 g/cm3, or notmore than 0.9 g/cm3, or not more than 0.85 g/cm3. In an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil exhibits a density at 15° C. at a range of 0.6 to 1 g/cm3, 0.65 to0.95 g/cm3, or 0.7 to 0.9 g/cm3.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may exhibit an API gravity at 15° C. of atleast 28, or at least 29, or at least 30, or at least 31, or at least32, or at least 33. Additionally, or alternatively, in an embodiment orin combination with any of the embodiments mentioned herein, thepyrolysis oil may exhibit an API gravity at 15° C. of not more than 50,or not more than 49, or not more than 48, or not more than 47, or notmore than 46, or not more than 45, or not more than 44. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil exhibits an API gravity at 15° C. at a range of 28 to 50,29 to 58, or 30 to 44.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a mid-boiling point of at least 75°C., or at least 80° C., or at least 85° C., or at least 90° C., or atleast 95° C., or at least 100° C., or at least 105° C., or at least 110°C., or at least 115° C. The values can be measured according to theprocedures described in either according to ASTM D-2887, or in theworking examples. A mid-boiling point having the stated value aresatisfied if the value is obtained under either method. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a mid-boilingpoint of not more than 250° C., or not more than 245° C., or not morethan 240° C., or not more than 235° C., or not more than 230° C., or notmore than 225° C., or not more than 220° C., or not more than 215° C.,or not more than 210° C., or not more than 205° C., or not more than200° C., or not more than 195° C., or not more than 190° C., or not morethan 185° C., or not more than 180° C., or not more than 175° C., or notmore than 170° C., or not more than 165° C., or not more than 160° C., 1or not more than 55° C., or not more than 150° C., or not more than 145°C., or not more than 140° C., or not more than 135° C., or not more than130° C., or not more than 125° C., or not more than 120° C. The valuescan be measured according to the procedures described in eitheraccording to ASTM D-2887, or in the working examples. A mid-boilingpoint having the stated value are satisfied if the value is obtainedunder either method. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a mid-boilingpoint in the range of 75 to 250° C., 90 to 225° C., or 115 to 190° C. Asused herein, “mid-boiling point” refers to the median boiling pointtemperature of the pyrolysis oil when 50 weight percent of the pyrolysisoil boils above the mid-boiling point and 50 weight percent boils belowthe mid-boiling point.

In an embodiment or in combination with any of the embodiments mentionedherein, the boiling point range of the pyrolysis oil may be such thatnot more than 10 percent of the pyrolysis oil has a final boiling point(FBP) of 250° C., 280° C., 290° C., 300° C., or 310° C., to determinethe FBP, the procedures described in either according to ASTM D-2887, orin the working examples, can be employed and a FBP having the statedvalues are satisfied if the value is obtained under either method.

Turning to the pyrolysis gas, the pyrolysis gas can have a methanecontent of at least 1, or at least 2, or at least 5, or at least 10, orat least 11, or at least 12, or at least 13, or at least 14, or at least15, or at least 16, or at least 17, or at least 18, or at least 19, orat least 20 weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a methane content of not more than50, or not more than 45, or not more than 40, or not more than 35, ornot more than 30, or not more than 25, in each case weight percent. Inan embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a methane content in the range of 1to 50 weight percent, 5 to 50 weight percent, or 15 to 45 weightpercent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a C3 hydrocarbon content of at least1, or at least 2, or at least 3, or at least 4, or at least 5, or atleast 6, or at least 7, or at least 8, or at least 9, or at least 10, orat least 15, or at least 20, or at least 25, in each case weightpercent. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisgas can have a C3 hydrocarbon content of not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,in each case weight percent. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis gas can have a C3hydrocarbon content in the range of 1 to 50 weight percent, 5 to 50weight percent, or 20 to 50 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a C4 hydrocarbon content of at least1, or at least 2, or at least 3, or at least 4, or at least 5, or atleast 6, or at least 7, or at least 8, or at least 9, or at least 10, orat least 11, or at least 12, or at least 13, or at least 14, or at least15, or at least 16, or at least 17, or at least 18, or at least 19, orat least 20, in each case weight percent. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis gas can have a C4hydrocarbon content of not more than 50, or not more than 45, or notmore than 40, or not more than 35, or not more than 30, or not more than25, in each case weight percent. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis gas can have a C4hydrocarbon content in the range of 1 to 50 weight percent, 5 to 50weight percent, or 20 to 50 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oils of the present invention may be a recyclecontent pyrolysis oil composition (r-pyoil).

Various downstream applications that may utilize the above-disclosedpyrolysis oils and/or the pyrolysis gases are described in greaterdetail below. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may be subjected to oneor more treatment steps prior to being introduced into downstream units,such as a cracking furnace. Examples of suitable treatment steps caninclude, but are not limited to, separation of less desirable components(e.g., nitrogen-containing compounds, oxygenates, and/or olefins andaromatics), distillation to provide specific pyrolysis oil compositions,and preheating.

Turning now to FIG. 3, a schematic depiction of a treatment zone forpyrolysis oil according to an embodiment or in combination with any ofthe embodiments mentioned herein is shown.

As shown in the treatment zone 220 illustrated in FIG. 3, at least aportion of the r-pyoil 252 made from a recycle waste stream 250 in thepyrolysis system 210 may be passed through a treatment zone 220 such as,for example, a separator, which may separate the r-pyoil into a lightpyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. Theseparator 220 employed for such a separation can be of any suitabletype, including a single-stage vapor liquid separator or “flash” column,or a multi-stage distillation column. The vessel may or may not includeinternals and may or may not employ a reflux and/or boil-up stream.

In an embodiment or in combination with any of the embodiments mentionedherein, the heavy fraction may have a C4 to C7 content or a C8+ contentof at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,or 85 weight percent. The light fraction may include at least about 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 percent ofC3 and lighter (C3-) or C7 and lighter (C7-) content. In someembodiments, separator may concentrate desired components into the heavyfraction, such that the heavy fraction may have a C4 to C7 content or aC8+content that is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 7, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140,145, or 150% greater than the C4 to C7 content or the C8+content of thepyrolysis oil withdrawn from the pyrolysis zone. As shown in FIG. 3, atleast a portion of the heavy fraction may be sent to the crackingfurnace 230 for cracking as or as part of the r-pyoil composition toform an olefin-containing effluent 258, as discussed in further detailbelow.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil is hydrotreated in a treatment zone, while, inother embodiments, the pyrolysis oil is not hydrotreated prior toentering downstream units, such as a cracking furnace. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil is not pretreated at all before any downstreamapplications and may be sent directly from the pyrolysis oil source. Thetemperature of the pyrolysis oil exiting the pre-treatment zone can bein the range of 15 to 55° C., 30 to 55° C., 49 to 40° C., 15 to 50° C.,20 to 45° C., or 25 to 40° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may be combined with the non-recycle cracker streamin order to minimize the amount of less desirable compounds present inthe combined cracker feed. For example, when the r-pyoil has aconcentration of less desirable compounds (such as, for example,impurities like oxygen-containing compounds, aromatics, or othersdescribed herein), the r-pyoil may be combined with a cracker feedstockin an amount such that the total concentration of the less desirablecompound in the combined stream is at least 40, 50, 55, 60, 65, 70, 75,80, 85, 90, or 95 percent less than the original content of the compoundin the r-pyoil stream (calculated as the difference between the r-pyoiland combined streams, divided by the r-pyoil content, expressed as apercentage). In some cases, the amount of non-recycle cracker feed tocombine with the r-pyoil stream may be determined by comparing themeasured amount of the one or more less desirable compounds present inthe r-pyoil with a target value for the compound or compounds todetermine a difference and, then, based on that difference, determiningthe amount of non-recycle hydrocarbon to add to the r-pyoil stream. Theamounts of r-pyoil and non-recycle hydrocarbon can be within one or moreranges described herein.

At least a portion of the r-ethylene can be derived directly orindirectly from the cracking of r-pyoil. The process for obtainingr-olefins from cracking (r-pyoil) can be as follows and as described inFIG. 4.

Turning now to FIG. 4, a block flow diagram illustrating stepsassociated with the cracking furnace 20 and separation zones 30 of asystem for producing an r-composition obtained from cracking r-pyoil. Asshown in FIG. 4, a feed stream comprising r-pyoil (the r-pyoilcontaining feed stream) may be introduced into a cracking furnace 20,alone or in combination with a non-recycle cracker feed stream. Apyrolysis unit producing r-pyoil can be co-located with the productionfacility. In other embodiments, the r-pyoil can be sourced from a remotepyrolysis unit and transported to the production facility.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing feed stream may contain r-pyoil in anamount of at least 1, or at least 5, or at least 10, or at least 15, orat least 20, or at least 25, or at least 30, or at least 35, or at least40, or at least 45, or at least 50, or at least 55, or at least 60, orat least 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, or at least 95, or at least 97, or at least 98, orat least 99, or at least or 100, in each case weight percent and/or notmore than 95, or not more than 90, or not more than 85, or not more than80, or not more than 75, or not more than 70, or not more than 65, ornot more than 60, or not more than 55, or not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,or not more than 25, or not more than 20, in each case weight percent,based on the total weight of the r-pyoil containing feed stream.

In an embodiment or in combination with any of the embodiments mentionedherein, at least 1, or at least 5, or at least 10, or at least 15, or atleast 20, or at least 25, or at least 30, or at least 35, or at least40, or at least 45, or at least 50, or at least 55, or at least 60, orat least 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90 or at least 97, or at least 98, or at least 99, or100, in each case weight percent and/or not more than 95, or not morethan 90, or not more than 85, or not more than 80, or not more than 75,or not more than 70, or not more than 65, or not more than 60, or notmore than 55, or not more than 50, or not more than 45, or not more than40, or not more than 35, or not more than 30, or not more than 25, ornot more than 20, or not more than 15 or not more than 10, in each caseweight percent of the r-pyoil is obtained from the pyrolysis of a wastestream. In an embodiment or in combination with any of the embodimentsmentioned herein, at least a portion of the r-pyoil is obtained frompyrolysis of a feedstock comprising plastic waste. Desirably, at least90, or at least 95, or at least 97, or at least 98, or at least 99, orat least or 100, in each case wt. %, of the r-pyoil is obtained frompyrolysis of a feedstock comprising plastic waste, or a feedstockcomprising at least 50 wt. % plastic waste, or a feedstock comprising atleast 80 wt. % plastic waste, or a feedstock comprising at least 90 wt.% plastic waste, or a feedstock comprising at least 95 wt. % plasticwaste.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can have any one or combination of the compositionalcharacteristics described above with respect to pyrolysis oil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may comprise at least 55, or at least 60, or atleast 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, or at least 95, in each case weight percent ofC4-C30 hydrocarbons, and as used herein, hydrocarbons include aliphatic,cycloaliphatic, aromatic, and heterocyclic compounds. In an embodimentor in combination with any of the embodiments mentioned herein, ther-pyoil can predominantly comprise C5-C25, C5-C22, or C5-C20hydrocarbons, or may comprise at least 55, 60, 65, 70, 75, 80, 85, 90,or 95 weight percent of C5-C25, C5-C22, or C5-C20 hydrocarbons.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil composition can comprise C4-C12 aliphatic compounds(branched or unbranched alkanes and alkenes including diolefins, andalicyclics) and C13-C22 aliphatic compounds in a weight ratio of morethan 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or atleast 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or atleast 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weightand based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil composition can comprise C13-C22 aliphatic compounds(branched or unbranched alkanes and alkenes including diolefins, andalicyclics) and C4-C12 aliphatic compounds in a weight ratio of morethan 1:1, or at least 1.25:1, or at least 1.5:1, or at least 2:1, or atleast 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or atleast 6:1, or at least 7:1, 10:1, 20:1, or at least 40:1, each by weightand based on the weight of the r-pyoil.

In an embodiment, the two aliphatic hydrocarbons (branched or unbranchedalkanes and alkenes, and alicyclics) having the highest concentration inthe r-pyoil are in a range of C5-C18, or C5-C16, or C5-C14, or C5-C10,or C5-C8, inclusive.

The r-pyoil can include one or more of paraffins, naphthenes or cyclicaliphatic hydrocarbons, aromatics, aromatic containing compounds,olefins, oxygenated compounds and polymers, heteroatom compounds orpolymers, and other compounds or polymers.

For example, in an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil may comprise at least 5, or atleast 10, or at least 15, or at least 20, or at least 25, or at least30, or at least 35, or at least 40, or at least 45, or at least 50, orat least 55, or at least 60, or at least 65, or at least 70, or at least75, or at least 80, or at least 85, or at least 90, or at least 95, ineach case weight percent and/or not more than 99, or not more than 97,or not more than 95, or not more than 93, or not more than 90, or notmore than 87, or not more than 85, or not more than 83, or not more than80, or not more than 78, or not more than 75, or not more than 70, ornot more than 65, or not more than 60, or not more than 55, or not morethan 50, or not more than 45, or not more than 40, or not more than 35,or not more than 30, or not more than 25, or not more than 20, or notmore than 15, in each case weight percent of paraffins (or linear orbranched alkanes), based on the total weight of the r-pyoil. In anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content in the range of 25to 90, 35 to 90, or 40 to 80, or 40-70, or 40-65 weight percent, or5-50, or 5 to 40, or 5 to 35, or 10- to 35, or 10 to 30, or 5 to 25, or5 to 20, in each case as wt. % based on the weight of the r-pyoilcomposition.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include naphthenes or cyclic aliphatichydrocarbons in amount of zero, or at least 1, or at least 2, or atleast 5, or at least 8, or at least 10, or at least 15, or at least 20,in each case weight percent and/or not more than 50, or not more than45, or not more than 40, or not more than 35, or not more than 30, ornot more than 25, or not more than 20, or not more than 15, or not morethan 10, or not more than 5, or not more than 2, or not more than 1, ornot more than 0.5, or no detectable amount, in each case weight percent.In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a naphthene content of not more than 5, ornot more than 2, or not more than 1 wt. %, or no detectable amount, ornaphthenes. Examples of ranges for the amount of naphthenes (or cyclicaliphatic hydrocarbons) contained in the r-pyoil is from 0-35, or 0-30,or 0-25, or 2-20, or 2-15, or 2-10, or 1-10, in each case as wt. % basedon the weight of the r-pyoil composition.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a paraffin to olefin weight ratio of atleast 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, orat least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1,or at least 1:1. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the r-pyoilmay have a paraffin to olefin weight ratio not more than 3:1, or notmore than 2.5:1, or not more than 2:1, or not more than 1.5:1, or notmore than 1.4:1, or not more than 1.3:1. In an embodiment or incombination with any of the embodiments mentioned herein, the r-pyoilmay have a paraffin to olefin weight ratio in the range of 0.2:1 to 5:1,or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1 to 4:1, or0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have an n-paraffin to i-paraffin weight ratio ofat least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1,or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the r-pyoil may have ann-paraffin to i-paraffin weight ratio of not more than 100:1, or notmore than 50:1, or not more than 40:1, or not more than 30:1. In anembodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have an n-paraffin to i-paraffin weight ratio inthe range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

In an embodiment, the r-pyoil comprises not more than 30, or not morethan 25, or not more than 20, or not more than 15, or not more than 10,or not more than 8, or not more than 5, or not more than 2, or not morethan 1, in each case weight percent of aromatics, based on the totalweight of the r-pyoil. As used herein, the term “aromatics” refers tothe total amount (in weight) of benzene, toluene, xylene, and styrene.The r-pyoil may include at least 1, or at least 2, or at least 5, or atleast 8, or at least 10, in each case weight percent of aromatics, basedon the total weight of the r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include aromatic containing compounds in anamount of not more than 30, or not more than 25, or not more than 20, ornot more than 15, or not more than 10, or not more than 8, or not morethan 5, or not more than 2, or not more than 1, in each case weight, ornot detectable, based on the total weight of the r-pyoil. Aromaticcontaining compounds includes the above-mentioned aromatics and anycompounds containing an aromatic moiety, such as terephthalate residuesand fused ring aromatics such as the naphthalenes andtetrahydronaphthalene.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include olefins in amount of at least 1, or atleast 2, or at least 5, or at least 8, or at least 10, or at least 15,or at least 20, or at least 30, or at least 40, or at least 45, or atleast 50, or at least 55, or at least 60, or at least or at least 65, ineach case weight percent olefins and/or not more than 85, or not morethan 80, or not more than 75, or not more than 70, or not more than 65,or not more than 60, or not more than 55, or not more than 50, or notmore than 45, or not more than 40, or not more than 35, or not more than30, or not more than 25, or not more than 20, or not more than 15, ornot more than 10, in each case weight percent, based on the weight of ar-pyoil. Olefins include mono- and di-olefins. Examples of suitableranges include olefins present in an amount ranging from 5 to 45, or10-35, or 15 to 30, or 40-85, or 45-85, or 50-85, or 55-85, or 60-85, or65-85, or 40-80, or 45-80, or 50-80, or 55-80, or 60-80, or 65-80,45-80, or 50-80, or 55-80, or 60-80, or 65-80, or 40-75, or 45-75, or50-75, or 55-75, or 60-75, or 65-75, or 40-70, or 45-70, or 50-70, or55-70, or 60-70, or 65-70, or 40-65, or 45-65, or 50-65, or 55-65, ineach case as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include oxygenated compounds or polymers inamount of zero or at least 0.01, or at least 0.1, or at least 1, or atleast 2, or at least 5, in each case weight percent and/or not more than20, or not more than 15, or not more than 10, or not more than 8, or notmore than 6, or not more than 5, or not more than 3, or not more than 2,in each case weight percent oxygenated compounds or polymers, based onthe weight of a r-pyoil. Oxygenated compounds and polymers are thosecontaining an oxygen atom. Examples of suitable ranges includeoxygenated compounds present in an amount ranging from 0-20, or 0-15, or0-10, or 0.01-10, or 1-10, or 2-10, or 0.01-8, or 0.1-6, or 1-6, or0.01-5, in each case as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the amount of oxygen atoms in the r-pyoil can be not more than 10, ornot more than 8, or not more than 5, or not more than 4, or not morethan 3, or not more than 2.75, or not more than 2.5, or not more than2.25, or not more than 2, or not more than 1.75, or not more than 1.5,or not more than 1.25, or not more than 1, or not more than 0.75, or notmore than 0.5, or not more than 0.25, or not more than 0.1, or not morethan 0.05, in each case wt. %, based on the weight of the r-pyoil.Examples of the amount of oxygen in the r-pyoil can be from 0-8, or 0-5,or 0-3, or 0-2.5 or 0-2, or 0.001-5, or 0.001-4, or 0.001-3, or0.001-2.75, or 0.001-2.5, or 0.001-2, or 0.001-1.5, or 0.001-1, or0.001-0.5, or 0.001-0.1, in each case as wt. % based on the weight ofthe r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include heteroatom compounds or polymers inamount of at least 1, or at least 2, or at least 5, or at least 8, or atleast 10, or at least 15, or at least 20, in each case weight percentand/or not more than 25, or not more than 20, or not more than 15, ornot more than 10, or not more than 8, or not more than 6, or not morethan 5, or not more than 3, or not more than 2, in each case weightpercent, based on the weight of a r-pyoil. A heterocompound or polymeris defined in this paragraph as any compound or polymer containingnitrogen, sulfur, or phosphorus. Any other atom is not regarded as aheteroatom for purposes of determining the quantity of heteroatoms,heterocompounds, or heteropolymers present in the r-pyoil. The r-pyoilcan contain heteroatoms present in an amount of not more than 5, or notmore than 4, or not more than 3, or not more than 2.75, or not more than2.5, or not more than 2.25, or not more than 2, or not more than 1.75,or not more than 1.5, or not more than 1.25, or not more than 1, or notmore than 0.75, or not more than 0.5, or not more than 0.25, or not morethan 0.1, or not more than 0.075, or not more than 0.05, or not morethan 0.03, or not more than 0.02, or not more than 0.01, or not morethan 0.008, or not more than 0.006, or not more than 0.005, or not morethan 0.003, or not more than 0.002, in each case wt. %, based on theweight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the solubility of water in the r-pyoil at 1 atm and 25° C. is less than2 wt. %, water, or not more than 1.5, or not more than 1, or not morethan 0.5, or not more than 0.1, or not more than 0.075, or not more than0.05, or not more than 0.025, or not more than 0.01, or not more than0.005, in each case wt. % water based on the weight of the r-pyoil.Desirably, the solubility of water in the r-pyoil is not more than 0.1wt. % based on the weight of the r-pyoil. In an embodiment or incombination with any embodiment mentioned herein, the r-pyoil containsnot more than 2 wt. %, water, or not more than 1.5, or not more than 1,or not more than 0.5, desirably or not more than 0.1, or not more than0.075, or not more than 0.05, or not more than 0.025, or not more than0.01, or not more than 0.005, in each case wt. % water based on theweight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the solids content in the r-pyoil does not exceed 1, or is not more than0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2,or not more than 0.15, or not more than 0.1, or not more than 0.05, ornot more than 0.025, or not more than 0.01, or not more than 0.005, ordoes not exceed 0.001, in each case wt. % solids based on the weight ofthe r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the sulfur content of the r-pyoil does not exceed 2.5 wt. %, or is notmore than 2, or not more than 1.75, or not more than 1.5, or not morethan 1.25, or not more than 1, or not more than 0.75, or not more than0.5, or not more than 0.25, or not more than 0.1, or not more than 0.05,desirably or not more than 0.03, or not more than 0.02, or not more than0.01, or not more than 0.008, or not more than 0.006, or not more than0.004, or not more than 0.002, or is not more than 0.001, in each casewt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil can have the following compositional content:

carbon atom content of at least 75 wt. %, or at least or at least 77, orat least 80, or at least 82, or at least 85, in each case wt. %, and/orup to 90, or up to 88, or not more than 86, or not more than 85, or notmore than 83, or not more than 82, or not more than 80, or not more than77, or not more than 75, or not more than 73, or not more than 70, ornot more than 68, or not more than 65, or not more than 63, or up to 60,in each case wt. %, desirably at least 82% and up to 93%, and/or

hydrogen atom content of at least 10 wt. %, or at least 13, or at least14, or at least 15, or at least 16, or at least 17, or at least 18, ornot more than 19, or not more than 18, or not more than 17, or not morethan 16, or not more than 15, or not more than 14, or not more than 13,or up to 11, in each case wt. %,

an oxygen atom content not to exceed 10, or not more than 8, or not morethan 5, or not more than 4, or not more than 3, or not more than 2.75,or not more than 2.5, or not more than 2.25, or not more than 2, or notmore than 1.75, or not more than 1.5, or not more than 1.25, or not morethan 1, or not more than 0.75, or not more than 0.5, or not more than0.25, or not more than 0.1, or not more than 0.05, in each case wt. %,

in each case based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the amount of hydrogen atoms in the r-pyoil can be in a range of from10-20, or 10-18, or 11-17, or 12-16 or 13-16, or 13-15, or 12-15, ineach case as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the metal content of the r-pyoil is desirably low, for example, not morethan 2 wt. %, or not more than 1, or not more than 0.75, or not morethan 0.5, or not more than 0.25, or not more than 0.2, or not more than0.15, or not more than 0.1, or not more than 0.05, in each case wt. %based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the alkali metal and alkaline earth metal or mineral content of ther-pyoil is desirably low, for example, not more than 2 wt. %, or notmore than 1, or not more than 0.75, or not more than 0.5, or not morethan 0.25, or not more than 0.2, or not more than 0.15, or not more than0.1, or not more than 0.05, in each case wt. % based on the weight ofthe r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the weight ratio of paraffin to naphthene in the r-pyoil can be at least1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or atleast 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, orat least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, orat least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or atleast 13:1, or at least 15:1, or at least 17:1, based on the weight ofthe r-pyoil.

In an embodiment or in combination with any embodiment mentioned herein,the weight ratio of paraffin and naphthene combined to aromatics can beat least 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, orat least 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1,or at least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1,or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1,or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1,based on the weight of the r-pyoil. In an embodiment or in combinationwith any embodiment mentioned herein, the ratio of paraffin andnaphthene combined to aromatics in the r-pyoil can be in a range of from50:1-1:1, or 40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or20:1-1:1, or 20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1,1:1-4:1, or 1:1-3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a boiling point curve defined by one ormore of its 10%, its 50%, and its 90% boiling points, as defined below.As used herein, “boiling point” refers to the boiling point of acomposition as determined by ASTM D2887 or according to the proceduredescribed in the working examples. A boiling point having the statedvalues are satisfied if the value is obtained under either method.Additionally, as used herein, an “x % boiling point,” refers to aboiling point at which x percent by weight of the composition boils pereither of these methods.

As used throughout, an x % boiling at a stated temperature means atleast x % of the composition boils at the stated temperature. In anembodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feed stream or compositioncan be not more than 350, or not more than 325, or not more than 300, ornot more than 295, or not more than 290, or not more than 285, or notmore than 280, or not more than 275, or not more than 270, or not morethan 265, or not more than 260, or not more than 255, or not more than250, or not more than 245, or not more than 240, or not more than 235,or not more than 230, or not more than 225, or not more than 220, or notmore than 215, not more than 200, not more than 190, not more than 180,not more than 170, not more than 160, not more than 150, or not morethan 140, in each case ° C. and/or at least 200, or at least 205, or atleast 210, or at least 215, or at least 220, or at least 225, or atleast 230, in each case ° C. and/or not more than 25, 20, 15, 10, 5, or2 weight percent of the r-pyoil may have a boiling point of 300° C. orhigher.

Referring again to FIG. 3, the r-pyoil may be introduced into a crackingfurnace or coil or tube alone (e.g., in a stream comprising at least 85,or at least 90, or at least 95, or at least 99, or 100, in each case wt.% percent pyrolysis oil based on the weight of the cracker feed stream),or combined with one or more non-recycle cracker feed streams. Whenintroduced into a cracker furnace, coil, or tube with a non-recyclecracker feed stream, the r-pyoil may be present in an amount of at least1, or at least 2, or at least 5, or at least 8, or at least 10, or atleast 12, or at least 15, or at least 20, or at least 25, or at least30, in each case wt. % and/or not more than 40, or not more than 35, ornot more than 30, or not more than 25, or not more than 20, or not morethan 15, or not more than 10, or not more than 8, or not more than 5, ornot more than 2, in each case weight percent based on the total weightof the combined stream. Thus, the non-recycle cracker feed stream orcomposition may be present in the combined stream in an amount of atleast 20, or at least 25, or at least 30, or at least 35, or at least40, or at least 45, or at least 50, or at least 55, or at least 60, orat least 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, in each case weight percent and/or not more than 99,or not more than 95, or not more than 90, or not more than 85, or notmore than 80, or not more than 75, or not more than 70, or not more than65, or not more than 60, or not more than 55, or not more than 50, ornot more than 45, or not more than 40, in each case weight percent basedon the total weight of the combined stream. Unless otherwise notedherein, the properties of the cracker feed stream as described belowapply either to the non-recycle cracker feed stream prior to (or absent)combination with the stream comprising r-pyoil, as well as to a combinedcracker stream including both a non-recycle cracker feed and a r-pyoilfeed.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream may comprise a predominantly C2-C4hydrocarbon containing composition, or a predominantly C5-C22hydrocarboncontaining composition. As used herein, the term “predominantly C2-C4hydrocarbon,” refers to a stream or composition containing at least 50weight percent of C2-C4 hydrocarbon components. Examples of specifictypes of C2-C4 hydrocarbon streams or compositions include propane,ethane, butane, and LPG. In an embodiment or in combination with any ofthe embodiments mentioned herein, the cracker feed may comprise at least50, or at least 55, or at least 60, or at least 65, or at least 70, orat least 75, or at least 80, or at least 85, or at least 90, or at least95, in each case wt. % based on the total weight of the feed, and/or notmore than 100, or not more than 99, or not more than 95, or not morethan 92, or not more than 90, or not more than 85, or not more than 80,or not more than 75, or not more than 70, or not more than 65, or notmore than 60, in each case weight percent C2-C4 hydrocarbons or linearalkanes, based on the total weight of the feed. The cracker feed cancomprise predominantly propane, predominantly ethane, predominantlybutane, or a combination of two or more of these components. Thesecomponents may be non-recycle components. The cracker feed can comprisepredominantly propane, or at least 50 mole % propane, or at least 80mole % propane, or at least 90 mole % propane, or at least 93 mole %propane, or at least 95 mole % propane (inclusive of any recycle streamscombined with virgin feed). The cracker feed can comprise HD5 qualitypropane as a virgin or fresh feed. The cracker can comprise at more than50 mole % ethane, or at least 80 mole % ethane, or at least 90 mole %ethane, or at least 95 mole % ethane. These components may benon-recycle components.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream may comprise a predominantly C5-C22hydrocarbon containing composition. As used herein, “predominantlyC5-C22 hydrocarbon” refers to a stream or composition comprising atleast 50 weight percent of C5-C22 hydrocarbon components. Examplesinclude gasoline, naphtha, middle distillates, diesel, kerosene. In anembodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream or composition may comprise at least 20,or at least 25, or at least 30, or at least 35, or at least 40, or atleast 45, or at least 50, or at least 55, or at least 60, or at least65, or at least 70, or at least 75, or at least 80, or at least 85, orat least 90, or at least 95, in each case wt. % and/or not more than100, or not more than 99, or not more than 95, or not more than 92, ornot more than 90, or not more than 85, or not more than 80, or not morethan 75, or not more than 70, or not more than 65, or not more than 60,in each case weight percent C5-C22, or C5-C20 hydrocarbons, based on thetotal weight of the stream or composition. In an embodiment or incombination with any of the embodiments mentioned herein, the crackerfeed may have a C15 and heavier (C15+) content of at least 0.5, or atleast 1, or at least 2, or at least 5, in each case weight percentand/or not more than 40, or not more than 35, or not more than 30, ornot more than 25, or not more than 20, or not more than 18, or not morethan 15, or not more than 12, or not more than 10, or not more than 5,or not more than 3, in each case weight percent, based on the totalweight of the feed.

The cracker feed may have a boiling point curve defined by one or moreof its 10%, its 50%, and its 90% boiling points, the boiling point beingobtained by the methods described above Additionally, as used herein, an“x % boiling point,” refers to a boiling point at which x percent byweight of the composition boils per the methods described above. In anembodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feed stream or compositioncan be not more than 360, or not more than 355, or not more than 350, ornot more than 345, or not more than 340, or not more than 335, or notmore than 330, or not more than 325, or not more than 320, or not morethan 315, or not more than 300, or not more than 295, or not more than290, or not more than 285, or not more than 280, or not more than 275,or not more than 270, or not more than 265, or not more than 260, or notmore than 255, or not more than 250, or not more than 245, or not morethan 240, or not more than 235, or not more than 230, or not more than225, or not more than 220, or not more than 215, in each case ° C.and/or at least 200, or at least 205, or at least 210, or at least 215,or at least 220, or at least 225, or at least 230, in each case ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 10% boiling point of the cracker feed stream or compositioncan be at least 40, at least 50, at least 60, at least 70, at least 80,at least 90, at least 100, at least 110, at least 120, at least 130, atleast 140, at least 150, or at least 155, in each case ° C. and/or notmore than 250, not more than 240, not more than 230, not more than 220,not more than 210, not more than 200, not more than 190, not more than180, or not more than 170 in each case ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 50% boiling point of the cracker feed stream or compositioncan be at least 60, at least 65, at least 70, at least 75, at least 80,at least 85, at least 90, at least 95, at least 100, at least 110, atleast 120, at least 130, at least 140, at least 150, at least 160, atleast 170, at least 180, at least 190, at least 200, at least 210, atleast 220, or at least 230, in each case ° C., and/or not more than 300,not more than 290, not more than 280, not more than 270, not more than260, not more than 250, not more than 240, not more than 230, not morethan 220, not more than 210, not more than 200, not more than 190, notmore than 180, not more than 170, not more than 160, not more than 150,or not more than 145° C. The 50% boiling point of the cracker feedstream or composition can be in the range of 65 to 160, 70 to 150, 80 to145, 85 to 140, 85 to 230, 90 to 220, 95 to 200, 100 to 190, 110 to 180,200 to 300, 210 to 290, 220 to 280, 230 to 270, in each case in ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feedstock or stream orcomposition can be at least 350° C., the 10% boiling point can be atleast 60° C.; and the 50% boiling point can be in the range of from 95°C. to 200° C. In an embodiment or in combination with any of theembodiments mentioned herein, the 90% boiling point of the crackerfeedstock or stream or composition can be at least 150° C., the 10%boiling point can be at least 60° C., and the 50% boiling point can bein the range of from 80 to 145° C. In an embodiment or in combinationwith any of the embodiments mentioned herein, the cracker feedstock orstream has a 90% boiling point of at least 350° C., a 10% boiling pointof at least 150° C., and a 50% boiling point in the range of from 220 to280° C.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil is cracked in a gas furnace. A gas furnace is a furnacehaving at least one coil which receives (or operated to receive), at theinlet of the coil at the entrance to the convection zone, apredominately vapor-phase feed (more than 50% of the weight of the feedis vapor) (“gas coil”). In an embodiment or in combination with anyembodiment mentioned herein, the gas coil can receive a predominatelyC2-C4 feedstock, or a predominately a C2-C3 feedstock to the inlet ofthe coil in the convection section, or alternatively, having at leastone coil receiving more than 50 wt. % ethane and/or more than 50%propane and/or more than 50% LPG, or in any one of these cases at least60 wt. %, or at least 70 wt. %, or at least 80 wt. %, based on theweight of the cracker feed to the coil, or alternatively based on theweight of the cracker feed to the convection zone. The gas furnace mayhave more than one gas coil. In an embodiment or in combination with anyembodiment mentioned herein, at least 25% of the coils, or at least 50%of the coils, or at least 60% of the coils, or all the coils in theconvection zone or within a convection box of the furnace are gas coils.In an embodiment or in combination with any embodiment mentioned herein,the gas coil receives, at the inlet of the coil at the entrance to theconvection zone, a vapor-phase feed in which at least 60 wt. %, or atleast 70 wt. %, or at least 80 wt. %, or at least 90 wt. %, or at least95 wt. %, or at least 97 wt. %, or at least 98 wt. %, or at least 99 wt.%, or at least 99.5 wt. %, or at least 99.9 wt. % of feed is vapor.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil is cracked in a split furnace. A split furnace is a type ofgas furnace. A split furnace contains at least one gas coil and at leastone liquid coil within the same furnace, or within the same convectionzone, or within the same convection box. A liquid coil is a coil whichreceives, at the inlet of coil at the entrance to the convection zone, apredominately liquid phase feed (more than 50% of the weight of the feedis liquid) (“liquid coil”). In an embodiment or in combination with anyembodiment mentioned herein, the liquid coil can receive a predominatelyC5+feedstock to the inlet of the coil at the entrance of the convectionsection (“liquid coil”). In an embodiment or in combination with anyembodiment mentioned herein, the liquid coil can receive a predominatelyC6-C22 feedstock, or a predominately a C7-C16 feedstock to the inlet ofthe coil in the convection section, or alternatively, having at leastone coil receiving more than 50 wt. % naphtha, and/or more than 50%natural gasoline, and/or more than 50% diesel, and/or more than JP-4,and/or more than 50% Stoddard Solvent, and/or more than 50% kerosene,and/or more than 50% fresh creosote, and/or more than 50% JP-8 or Jet-A,and/or more than 50% heating oil, and/or more than 50% heavy fuel oil,and/or more than 50% bunker C, and/or more than 50% lubricating oil, orin any one of these cases at least 60 wt. %, or at least 70 wt. %, or atleast 80 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least98 wt. %, or at least 99 wt. %, based on the weight of the cracker feedto the liquid coil, or alternatively based on the weight of the crackerfeed to the convection zone. In an embodiment or in combination with anyembodiment mentioned herein, at least one coil and not more than 75% ofthe coils, or not more than 50% of the coils, or not more than at least40% of the coils in the convection zone or within a convection box ofthe furnace are liquid coils. In an embodiment or in combination withany embodiment mentioned herein, the liquid coil receives, at the inletof the coil at the entrance to the convection zone, a liquid-phase feedin which at least 60 wt. %, or at least 70 wt. %, or at least 80 wt. %,or at least 90 wt. %, or at least 95 wt. %, or at least 97 wt. %, or atleast 98 wt. %, or at least 99 wt. %, or at least 99.5 wt. %, or atleast 99.9 wt. % of feed is liquid.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil is cracked in a thermal gas cracker.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil is cracked in a thermal steam gas cracker in the presence ofsteam. Steam cracking refers to the high-temperature cracking(decomposition) of hydrocarbons in the presence of steam.

In an embodiment or in combination with any embodiment mentioned herein,the r-composition is derived directly or indirectly from crackingr-pyoil in a gas furnace. The coils in the gas furnace can consistentirely of gas coils or the gas furnace can be a split furnace.

When the r-pyoil containing feed stream is combined with the non-recyclecracker feed, such a combination may occur upstream of, or within, thecracking furnace or within a single coil or tube. Alternatively, ther-pyoil containing feed stream and non-recycle cracker feed may beintroduced separately into the furnace, and may pass through a portion,or all, of the furnace simultaneously while being isolated from oneanother by feeding into separate tubes within the same furnace (e.g., asplit furnace). Ways of introducing the r-pyoil containing feed streamand the non-recycle cracker feed into the cracking furnace according toan embodiment or in combination with any of the embodiments mentionedherein are described in further detail below.

Turning now to FIG. 5, a schematic diagram of a cracker furnace suitablefor use in an embodiment or in combination with any of the embodimentsmentioned herein is shown.

In one embodiment or in combination of any of the mentioned embodiments,there is provided a method for making one or more olefins including:

(a) feeding a first cracker feed comprising a recycle content pyrolysisoil composition (r-pyoil) to a cracker furnace;

(b) feeding a second cracker feed into said cracker furnace, whereinsaid second cracker feed comprises none of said r-pyoil or less of saidr-pyoil, by weight, than said first cracker feed stream; and

(c) cracking said first and said second cracker feeds in respectivefirst and second tubes to form an olefin-containing effluent stream.

The r-pyoil can be combined with a cracker stream to make a combinedcracker stream, or as noted above, a first cracker stream. The firstcracker stream can be 100% r-pyoil or a combination of a non-recyclecracker stream and r-pyoil. The feeding of step (a) and/or step (b) canbe performed upstream of the convection zone or within the convectionzone. The r-pyoil can be combined with a non-recycle cracker stream toform a combined or first cracker stream and fed to the inlet of aconvection zone, or alternatively the r-pyoil can be separately fed tothe inlet of a coil or distributor along with a non-recycle crackerstream to form a first cracker stream at the inlet of the convectionzone, or the r-pyoil can be fed downstream of the inlet of theconvection zone into a tube containing non-recycle cracker feed, butbefore a crossover, to make a first cracker stream or combined crackerstream in a tube or coil. Any of these methods includes feeding thefirst cracker stream to the furnace.

The amount of r-pyoil added to the non-recycle cracker stream to makethe first cracker stream or combined cracker stream can be as describedabove; e.g. in an amount of at least 1, 5, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, in each case weightpercent and/or not more than 95, 90, 85, 80, 75, 70, 65, 60, 55, 60, 55,50, 45, 40, 35, 30, 25, 20, 15, or 1, in each case weight percent, basedon the total weight of the first cracker feed or combined cracker feed(either as introduced into the tube or within the tube as noted above).Further examples include 5-50, 5-40, 5-35, 5-30, 5-25, 5-20, or 5-15 wt.%.

The first cracker stream is cracked in a first coil or tube. The secondcracker stream is cracked in a second coil or tube. Both the first andsecond cracker streams and the first and second coils or tubes can bewithin the same cracker furnace.

The second cracker stream can have none of the r-pyoil or less of saidr-pyoil, by weight, than the first cracker feed stream. Also, the secondcracker stream can contain only non-recycle cracker feed in the secondcoil or tube. The second cracker feed stream can be predominantly C2 toC4, or hydrocarbons (e.g. non-recycle content), or ethane, propane, orbutane, in each case in amounts of at least 55, 60, 65, 70, 75, 80, 85,or at least 90 weight percent based on the second cracker feed within asecond coil or tube. If r-pyoil is included in the second cracker feed,the amount of such r-pyoil can be at least 10% less, 20, 30, 40, 50, 60,70, 80, 90, 95, 97, or 99% less by weight than the amount of r-pyoil inthe first cracker feed.

In an embodiment or in combination with any embodiment mentioned herein,although not shown, a vaporizer can be provided to vaporize a condensedfeedstock of C2-C5 hydrocarbons 350 to ensure that the feed to the inletof the coils in the convection box 312, or the inlet of the convectionzone 310, is a predominately vapor phase feed.

The cracking furnace shown in FIG. 5 includes a convection section orzone 310, a radiant section or zone 320, and a cross-over section orzone 330 located between the convection and radiant sections 310 and320. The convection section 310 is the portion of the furnace 300 thatreceives heat from hot flue gases and includes a bank of tubes or coils324 through which a cracker stream 350 passes. In the convection section310, the cracker stream 350 is heated by convection from the hot fluegasses passing therethrough. The radiant section 320 is the section ofthe furnace 300 into which heat is transferred into the heater tubesprimarily by radiation from the high-temperature gas. The radiantsection 320 also includes a plurality of burners 326 for introducingheat into the lower portion of the furnace. The furnace includes a firebox 322 which surrounds and houses the tubes within the radiant section320 and into which the burners are oriented. The cross-over section 330includes piping for connecting the convection 310 and radiant sections320 and may transfer the heated cracker stream internally or externallyfrom one section to the other within the furnace 300.

As hot combustion gases ascend upwardly through the furnace stack, thegases may pass through the convection section 310, wherein at least aportion of the waste heat may be recovered and used to heat the crackerstream passing through the convection section 310. In an embodiment orin combination with any of the embodiments mentioned herein, thecracking furnace 300 may have a single convection (preheat) section 310and a single radiant 320 section, while, in other embodiments, thefurnace may include two or more radiant sections sharing a commonconvection section. At least one induced draft (I.D.) fan 316 near thestack may control the flow of hot flue gas and heating profile throughthe furnace, and one or more heat exchangers 340 may be used to cool thefurnace effluent 370. In an embodiment or in combination with any of theembodiments mentioned herein (not shown), a liquid quench may be used inaddition to, or alternatively with, the exchanger (e.g., transfer lineheat exchanger or TLE) shown in FIG. 5, for cooling the crackedolefin-containing effluent.

The furnace 300 also includes at least one furnace coil 324 throughwhich the cracker streams pass through the furnace. The furnace coils324 may be formed of any material inert to the cracker stream andsuitable for withstanding high temperatures and thermal stresses withinthe furnace. The coils may have any suitable shape and can, for example,have a circular or oval cross-sectional shape.

The coils in the convection section 310, or tubes within the coil, mayhave a diameter of at least 1, or at least 1.5, or at least 2, or atleast 2.5, or at least 3, or at least 3.5, or at least 4, or at least4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5, orat least 7, or at least 7.5, or at least 8, or at least 8.5, or at least9, or at least 9.5, or at least 10, or at least 10.5, in each case cmand/or not more than 12, or not more than 11.5, or not more than 11, 1or not more than 0.5, or not more than 10, or not more than 9.5, or notmore than 9, or not more than 8.5, or not more than 8, or not more than7.5, or not more than 7, or not more than 6.5, in each case cm. All or aportion of one or more coils can be substantially straight, or one ormore of the coils may include a helical, twisted, or spiral segment. Oneor more of the coils may also have a U-tube or split U-tube design. Inan embodiment or in combination with any of the embodiments mentionedherein, the interior of the tubes may be smooth or substantially smooth,or a portion (or all) may be roughened in order to minimize coking.Alternatively, or in addition, the inner portion of the tube may includeinserts or fins and/or surface metal additives to prevent coke build up.

In an embodiment or in combination with any of the embodiments mentionedherein, all or a portion of the furnace coil or coils 324 passingthrough in the convection section 310 may be oriented horizontally,while all, or at least a portion of, the portion of the furnace coilpassing through the radiant section 322 may be oriented vertically. Inan embodiment or in combination with any of the embodiments mentionedherein, a single furnace coil may run through both the convection andradiant section. Alternatively, at least one coil may split into two ormore tubes at one or more points within the furnace, so that crackerstream may pass along multiple paths in parallel. For example, thecracker stream (including r-pyoil) 350 may be introduced into multiplecoil inlets in the convection zone 310, or into multiple tube inlets inthe radiant 320 or cross-over sections 330. When introduced intomultiple coil or tube inlets simultaneously, or nearly simultaneously,the amount of r-pyoil introduced into each coil or tube may not beregulated. In an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil and/or cracker stream may beintroduced into a common header, which then channels the r-pyoil intomultiple coil or tube inlets.

A single furnace can have at least 1, or at least 2, or at least 3, orat least 4, or at least 5, or at least 6, or at least 7, or at least 8or more, in each case coils. Each coil can be from 5 to 100, 10 to 75,or 20 to 50 meters in length and can include at least 1, or at least 2,or at least 3, or at least 4, or at least 5, or at least 6, or at least7, or at least 8, or at least 10, or at least 12, or at least 14 or moretubes. Tubes of a single coil may be arranged in many configurations andin an embodiment or in combination with any of the embodiments mentionedherein may be connected by one or more 1800 (“U”) bends. One example ofa furnace coil 410 having multiple tubes 420 is shown in FIG. 6.

An olefin plant can have a single cracking furnace, or it can have atleast 2, or at least 3, or at least 4, or at least 5, or at least 6, orat least 7, or at least 8 or more cracking furnaces operated inparallel. Any one or each furnace(s) may be gas cracker, or a liquidcracker, or a split furnace. In an embodiment or in combination with anyembodiment mentioned herein, the furnace is a gas cracker receiving acracker feed stream containing at least 50 wt. %, or at least 75 wt. %,or at least 85 wt. % or at least 90 wt. % ethane, propane, LPG, or acombination thereof through the furnace, or through at least one coil ina furnace, or through at least one tube in the furnace, based on theweight of all cracker feed to the furnace. In an embodiment or incombination with any embodiment mentioned herein, the furnace is aliquid or naphtha cracker receiving a cracker feed stream containing atleast 50 wt. %, or at least 75 wt. %, or at least 85 wt. % liquid (whenmeasured at 25° C. and 1 atm) hydrocarbons having a carbon number fromC5-C22. through the furnace, or through at least one coil in a furnace,or through at least one tube in the furnace, based on the weight of allcracker feed to the furnace. In an embodiment or in combination with anyembodiment mentioned herein, the cracker is a split furnace receiving acracker feed stream containing at least 50 wt. %, or at least 75 wt. %,or at least 85 wt. % or at least 90 wt. % ethane, propane, LPG, or acombination thereof through the furnace, or through at least one coil ina furnace, or through at least one tube in the furnace, and receiving acracker feed stream containing at least 0.5 wt. %, or at least 0.1 wt.%, or at least 1 wt. %, or at least 2 wt. %, or at least 5 wt. %, or atleast 7 wt. %, or at least 10 wt. %, or at least 13 wt. %, or at least15 wt. %, or at least 20 wt. % liquid and/or r-pyoil (when measured at25° C. and 1 atm), each based on the weight of all cracker feed to thefurnace.

Turning now to FIG. 7, several possible locations for introducing ther-pyoil containing feed stream and the non-recycle cracker feed streaminto a cracking furnace are shown.

In an embodiment or in combination with any of the embodiments mentionedherein, an r-pyoil containing feed stream 550 may be combined with thenon-recycle cracker feed 552 upstream of the convection section to forma combined cracker feed stream 554, which may then be introduced intothe convection section 510 of the furnace. Alternatively, or inaddition, the r-pyoil containing feed 550 may be introduced into a firstfurnace coil, while the non-recycle cracker feed 552 is introduced intoa separate or second furnace coil, within the same furnace, or withinthe same convection zone. Both streams may then travel in parallel withone another through the convection section 510 within a convection box512, cross-over 530, and radiant section 520 within a radiant box 522,such that each stream is substantially fluidly isolated from the otherover most, or all, of the travel path from the inlet to the outlet ofthe furnace. The pyoil stream introduced into any heating zone withinthe convection section 510 can flow through the convection section 510and flow through as a vaporized stream 514 b into the radiant box 522.In other embodiments, the r-pyoil containing feed stream 550 may beintroduced into the non-recycle cracker stream 552 as it passes througha furnace coil in the convection section 510 flowing into the cross-oversection 530 of the furnace to form a combined cracker stream 514 a, asalso shown in FIG. 7.

In an embodiment or in combination with any embodiment mentioned herein,the r-pyoil 550 may be introduced into the first furnace coil, or anadditional amount introduced into the second furnace coil, at either afirst heating zone or a second heating zone as shown in FIG. 7. Ther-pyoil 550 may be introduced into the furnace coil at these locationsthrough a nozzle. A convenient method for introducing the feed ofr-pyoil is through one or more dilution steam feed nozzles that are usedto feed steam into the coil in the convection zone. The service of oneor more dilution steam nozzles may be employed to inject r-pyoil, or anew nozzle can be fastened to the coil dedicated to the injection of ther-pyoil. In an embodiment or in combination with any embodimentmentioned herein, both steam and r-pyoil can be co-fed through a nozzleinto the furnace coil downstream of the inlet to the coil and upstreamof a crossover, optionally at the first or second heating zone withinthe convection zone as shown in FIG. 7.

The non-recycle cracker feed stream may be mostly liquid and have avapor fraction of less than 0.25 by volume, or less than 0.25 by weight,or it may be mostly vapor and have a vapor fraction of at least 0.75 byvolume, or at least 0.75 by weight, when introduced into the furnaceand/or when combined with the r-pyoil containing feed. Similarly, ther-pyoil containing feed may be mostly vapor or mostly liquid whenintroduced into the furnace and/or when combined with the non-recyclecracker stream.

In an embodiment or in combination with any of the embodiments mentionedherein, at least a portion or all of the r-pyoil stream or cracker feedstream may be preheated prior to being introduced into the furnace. Asshown in FIG. 8, the preheating can be performed with an indirect heatexchanger 618 heated by a heat transfer media (such as steam, hotcondensate, or a portion of the olefin-containing effluent) or via adirect fired heat exchanger 618. The preheating step can vaporize all ora portion of the stream comprising r-pyoil and may, for example,vaporize at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weightpercent of the stream comprising r-pyoil.

The preheating, when performed, can increase the temperature of ther-pyoil containing stream to a temperature that is within about 50, 45,40, 35, 30, 25, 20, 15, 10, 5, or 2° C. of the bubble point temperatureof the r-pyoil containing stream. Additionally, or in the alternative,the preheating can increase the temperature of the stream comprisingr-pyoil to a temperature at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 85, 90, or 100° C. below the coking temperatureof the stream. In an embodiment or in combination with any of theembodiments mentioned herein, the preheated r-pyoil stream can have atemperature of at least 200, 225, 240, 250, or 260° C. and/or not morethan 375, 350, 340, 330, 325, 320, or 315° C., or at least 275, 300,325, 350, 375, or 400° C. and/or not more than 600, 575, 550, 525, 500,or 475° C. When the atomized liquid (as explained below) is injectedinto the vapor phase, heated cracker stream, the liquid may rapidlyevaporate such that, for example, the entire combined cracker stream isvapor (e.g., 100 percent vapor) within 5, 4, 3, 2, or 1 second afterinjection.

In an embodiment or in combination with any of the embodiments mentionedherein, the heated r-pyoil stream (or cracker stream comprising ther-pyoil and the non-recycle cracker stream) can optionally be passedthrough a vapor-liquid separator to remove any residual heavy or liquidcomponents, when present. The resulting light fraction may then beintroduced into the cracking furnace, alone or in combination with oneor more other cracker streams as described in various embodimentsherein. For example, in an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil stream can comprise at least1, 2, 5, 8, 10, or 12 weight percent C15 and heavier components. Theseparation can remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,or 99 weight percent of the heavier components from the r-pyoil stream.

Turning back to FIG. 7, the cracker feed stream (either alone or whencombined with the r-pyoil feed stream) may be introduced into a furnacecoil at or near the inlet of the convection section. The cracker streammay then pass through at least a portion of the furnace coil in theconvection section 510, and dilution steam may be added at some point inorder to control the temperature and cracking severity in the furnace.In an embodiment or in combination with any of the embodiments mentionedherein, the steam may be added upstream of or at the inlet to theconvection section, or it may be added downstream of the inlet to theconvection section—either in the convection section, at the cross-oversection, or upstream of or at the inlet to the radiant section.Similarly, the stream comprising the r-pyoil and the non-recycle crackerstream (alone or combined with the steam) may also be introduced into orupstream or at the inlet to the convection section, or downstream of theinlet to the convection section—either within the convection section, atthe cross-over, or at the inlet to the radiant section. The steam may becombined with the r-pyoil stream and/or cracker stream and the combinestream may be introduced at one or more of these locations, or the steamand r-pyoil and/or non-recycle cracker stream may be added separately.

When combined with steam and fed into or near the cross-over section ofthe furnace, the r-pyoil and/or cracker stream can have a temperature of500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630,640, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830, 820,810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695,690, 685, 680, 675, 670, 665, 660, 655, or 650° C. The resulting steamand r-pyoil stream can have a vapor fraction of at least 0.75, 0.80,0.85, 0.90, or at least 0.95 by weight, or at least 0.75, 0.80, 0.85,0.90, and 0.95 by volume.

When combined with steam and fed into or near the inlet to theconvection section 510, the r-pyoil and/or cracker stream can have atemperature of at least 30, 35, 40, 45, 50, 55, 60, or 65 and/or notmore than 100, 90, 80, 70, 60, 50, or 45° C.

The amount of steam added may depend on the operating conditions,including feed type and desired product, but can be added to achieve asteam-to-hydrocarbon ratio can be at least 0.10:1, 0.15:1, 0.20:1,0.25:1, 0.27:1, 0.30:1, 0.32:1, 0.35:1, 0.37:1, 0.40:1, 0.42:1, 0.45:1,0.47:1, 0.50:1, 0.52:1, 0.55:1, 0.57:1, 0.60:1, 0.62:1, 0.65:1 and/ornot more than about 1:1. 0.95:1, 0.90:1, 0.85:1, 0.80:1, 0.75:1, 0.72:1,0.70:1, 0.67:1, 0.65:1, 0.62:1, 0.60:1, 0.57:1, 0.55:1, 0.52:1, 0.50:1,or it can be in the range of from 0.1:1 to 1.0:1, 0.15:1 to 0.9:1, 0.2:1to 0.8:1, 0.3:1 to 0.75:1, or 0.4:1 to 0.6:1. When determining the“steam-to-hydrocarbon” ratio, all hydrocarbon components are includedand the ratio is by weight. In an embodiment or in combination with anyof the embodiments mentioned herein, the steam may be produced usingseparate boiler feed water/steam tubes heated in the convection sectionof the same furnace (not shown in FIG. 7). Steam may be added to thecracker feed (or any intermediate cracker stream within the furnace)when the cracker stream has a vapor fraction of 0.60 to 0.95, or 0.65 to0.90, or 0.70 to 0.90.

When the r-pyoil containing feed stream is introduced into the crackingfurnace separately from a non-recycle feed stream, the molar flow rateof the r-pyoil and/or the r-pyoil containing stream may be differentthan the molar flow rate of the non-recycle feed stream. In oneembodiment or in combination with any other mentioned embodiment, thereis provided a method for making one or more olefins by:

(a) feeding a first cracker stream having r-pyoil to a first tube inletin a cracker furnace;

(b) feeding a second cracker stream containing, or predominatelycontaining C₂ to C₄ hydrocarbons to a second tube inlet in the crackerfurnace, wherein said second tube is separate from said first tube andthe total molar flow rate of the first cracker stream fed at the firsttube inlet is lower than the total molar flow rate of the second crackerstream to the second tube inlet, calculated without the effect of steam.The feeding of step (a) and step (b) can be to respective coil inlets.

For example, the molar flow rate of the r-pyoil or the first crackerstream as it passes through a tube in the cracking furnace may be atleast 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or60 percent lower than the flow rate of the hydrocarbon components (e.g.,C2-C4 or C5-C22) components in the non-recycle feed stream, or thesecond cracker stream, passing through another or second tube. Whensteam is present in both the r-pyoil containing stream, or first crackerstream, and in the second cracker stream or the non-recycle feed stream,the total molar flow rate of the r-pyoil containing stream, or firstcracker stream, (including r-pyoil and dilution steam) may be at least5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or 60percent higher than the total molar flow rate (including hydrocarbon anddilution steam) of the non-recycle cracker feedstock, or second crackerstream (wherein the percentage is calculated as the difference betweenthe two molar flow rates divided by the flow rate of the non-recyclestream).

In an embodiment or in combination with any of the embodiments mentionedherein, the molar flow rate of the r-pyoil in the r-pyoil containingfeed stream (first cracker stream) within the furnace tube may be atleast 0.01, 0.02, 0.025, 0.03, 0.035 and/or not more than 0.06, 0.055,0.05, 0.045 kmol-lb/hr lower than the molar flow rate of the hydrocarbon(e.g., C2-C4 or C5-C22) in the non-recycle cracker stream (secondcracker stream). In an embodiment or in combination with any of theembodiments mentioned herein, the molar flow rates of the r-pyoil andthe cracker feed stream may be substantially similar, such that the twomolar flow rates are within 0.005, 0.001, or 0.0005 kmol-lb/hr of oneanother. The molar flow rate of the r-pyoil in the furnace tube can beat least 0.0005, 0.001, 0.0025, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 kilomoles-pound per hour (kmol-lb/hr) and/or not more than 0.25, 0.24, 0.23,0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.08, 0.05,0.025, 0.01, or 0.008 kmol-lb/hr, while the molar flow rate of thehydrocarbon components in the other coil or coils can be at least 0.02,0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14,0.15, 0.16, 0.17, 0.18 and/or not more than 0.30, 0.29, 0.28, 0.27,0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15kmol-lb/hr.

In an embodiment or in combination with any of the embodiments mentionedherein, the total molar flow rate of the r-pyoil containing stream(first cracker stream) can be at least 0.01, 0.02, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09 and/or not more than 0.30, 0.25, 0.20, 0.15,0.13, 0.10, 0.09, 0.08, 0.07, or 0.06 kmol-lb/hr lower than the totalmolar flow rate of the non-recycle feed stream (second cracker stream),or the same as the total molar flow rate of the non-recycle feed stream(second cracker stream). The total molar flow rate of the r-pyoilcontaining stream (first cracker stream) can be at least 0.01, 0.02,0.03, 0.04, 0.05, 0.06, 0.07 and/or not more than 0.10, 0.09, 0.08,0.07, or 0.06 kmol-lb/hr higher than the total molar flow rate of thesecond cracker stream, while the total molar flow rate of thenon-recycle feed stream (second cracker stream) can be at least 0.20,0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32,0.33 and/or not more than 0.50, 0.49, 0.48, 0.47. 0.46, 0.45, 0.44,0.43, 0.42, 0.41, 0.40 kmol-lb/hr.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing stream, or first cracker stream, has asteam-to-hydrocarbon ratio that is at least 5, 10, 15, 20, 25, 30, 35,40, 45, 50, 55, 60, 65, 70, 75, or 80 percent different than thesteam-to-hydrocarbon ratio of the non-recycle feed stream, or secondcracker stream. The steam-to-hydrocarbon ratio can be higher or lower.For example, the steam-to-hydrocarbon ratio of the r-pyoil containingstream or first cracker stream can be at least 0.01, 0.025, 0.05, 0.075,0.10, 0.125, 0.15, 0.175, or 0.20 and/or not more than 0.3, 0.27, 0.25,0.22, or 0.20 different than the steam-to-hydrocarbon ratio of thenon-recycle feed stream or second cracker stream. Thesteam-to-hydrocarbon ratio of the r-pyoil containing stream or firstcracker stream can be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45,0.47, 0.5 and/or not more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55,0.52, or 0.5, and the steam-to-hydrocarbon ratio of the non-recyclecracker feed or second cracker stream can be at least 0.02, 0.05, 0.07,0.10, 0.12, 0.15, 0.17, 0.20, 0.25 and/or not more than 0.45, 0.42,0.40, 0.37, 0.35, 0.32, or 0.30.

In an embodiment or in combination with any embodiments mentionedherein, the temperature of the r-pyoil containing stream as it passesthrough a cross-over section in the cracking furnace can be differentthan the temperature of the non-recycle cracker feed as it passesthrough the cross-over section, when the streams are introduced into andpassed through the furnace separately. For example, the temperature ofthe r-pyoil stream as it passes through the cross-over section may be atleast 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, or 75 percent different than the temperature of thenon-recycle hydrocarbon stream (e.g., C2-C4 or C5-C22) passing throughthe cross-over section in another coil. The percentage can be calculatedbased on the temperature of the non-recycle stream according to thefollowing formula:

[(temperature of r-pyoil stream−temperature of non-recycle crackerstream)]/(temperature of non-recycle cracker steam), expressed as apercentage.

The difference can be higher or lower. The average temperature of ther-pyoil containing stream at the cross-over section can be at least 400,425, 450, 475, 500, 525, 550, 575, 580, 585, 590, 595, 600, 605, 610,615, 620, or 625° C. and/or not more than 705, 700, 695, 690, 685, 680,675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525, or 500° C., whilethe average temperature of the non-recycle cracker feed can be at least401, 426, 451, 476, 501, 526, 551, 560, 565, 570, 575, 580, 585, 590,595, 600, 605, 610, 615, 620, or 625° C. and/or not more than 705, 700,695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550,525, or 500° C.

The heated cracker stream, which usually has a temperature of at least500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630,640, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830, 820,810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695,690, 685, 680, 675, 670, 665, 660, 655, or 650° C., or in the range offrom 500 to 710° C., 620 to 740° C., 560 to 670° C., or 510 to 650° C.,may then pass from the convection section of the furnace to the radiantsection via the cross-over section.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing feed stream may be added to the crackerstream at the cross-over section. When introduced into the furnace inthe cross-over section, the r-pyoil may be at least partially vaporizedby, for example, preheating the stream in a direct or indirect heatexchanger. When vaporized or partially vaporized, the r-pyoil containingstream has a vapor fraction of at least 0.5, 0.55, 0.6, 0.65, 0.7, 0.75,0.8, 0.85, 0.9, 0.95, or 0.99 by weight, or in one embodiment or incombination with any mentioned embodiments, by volume.

When the r-pyoil containing stream is atomized prior to entering thecross-over section, the atomization can be performed using one or moreatomizing nozzles. The atomization can take place within or outside thefurnace. In an embodiment or in combination with any of the embodimentsmentioned herein, an atomizing agent may be added to the r-pyoilcontaining stream during or prior to its atomization. The atomizingagent can include steam, or it may include predominantly ethane,propane, or combinations thereof. When used the atomizing agent may bepresent in the stream being atomized (e.g., the r-pyoil containingcomposition) in an amount of at least 1, 2, 4, 5, 8, 10, 12, 15, 10, 25,or 30 weight percent and/or not more than 50, 45, 40, 35, 30, 25, 20,15, or 10 weight percent.

The atomized or vaporized stream of r-pyoil may then be injected into orcombined with the cracker stream passing through the cross-over section.At least a portion of the injecting can be performed using at least onespray nozzle. At least one of the spray nozzles can be used to injectthe r-pyoil containing stream into the cracker feed stream may beoriented to discharge the atomized stream at an angle within about 45,50, 35, 30, 25, 20, 15, 10, 5, or 0° from the vertical. The spray nozzleor nozzles may also be oriented to discharge the atomized stream into acoil within the furnace at an angle within about 30, 25, 20, 15, 10, 8,5, 2, or 1° of being parallel, or parallel, with the axial centerline ofthe coil at the point of introduction. The step of injecting theatomized r-pyoil may be performed using at least two, three, four, five,six or more spray nozzles, in the cross-over and/or convection sectionof the furnace.

In an embodiment or in combination with any embodiments mentionedherein, atomized r-pyoil can be fed, alone or in combination with an atleast partially non-recycle cracker stream, into the inlet of one ormore coils in the convection section of the furnace. The temperature ofsuch an atomization can be at least 30, 35, 40, 45, 50, 55, 60, 65, 70,75, or 80° C. and/or not more than 120, 110, 100, 90, 95, 80, 85, 70,65, 60, or 55° C.

In an embodiment or in combination with any embodiments mentionedherein, the temperature of the atomized or vaporized stream can be atleast 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175,200, 225, 250, 275, 300, 325, 350° C. and/or not more than 550, 525,500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175,150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30, or 25° C. coolerthan the temperature of the cracker stream to which it is added. Theresulting combined cracker stream comprises a continuous vapor phasewith a discontinuous liquid phase (or droplets or particles) dispersedtherethrough. The atomized liquid phase may comprise r-pyoil, while thevapor phase may include predominantly C2-C4 components, ethane, propane,or combinations thereof. The combined cracker stream may have a vaporfraction of at least 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 0.99 by weight,or in one embodiment or in combination with any mentioned embodiments,by volume.

The temperature of the cracker stream passing through the cross-oversection can be at least 500, 510, 520, 530, 540, 550, 555, 560, 565,570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620, 625, 630, 635,640, 645, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830,820, 810, 800, 795, 790, 785, 780, 775, 770, 765, 760, 755, 750, 745,740, 735, 730, 725, 720, 715, 710, 705, 700, 695, 690, 685, 680, 675,670, 665, 660, 655, 650, 645, 640, 635, or 630° C., or in the range offrom 620 to 740° C., 550 to 680° C., 510 to 630° C.

The resulting cracker feed stream then passes into the radiant section.In an embodiment or in combination with any of the embodiments mentionedherein, the cracker stream (with or without the r-pyoil) from theconvection section may be passed through a vapor-liquid separator toseparate the stream into a heavy fraction and a light fraction beforecracking the light fraction further in the radiant section of thefurnace. One example of this is illustrated in FIG. 8.

In an embodiment or in combination with any of the embodiments mentionedherein, the vapor-liquid separator 640 may comprise a flash drum, whilein other embodiments it may comprise a fractionator. As the stream 614passes through the vapor-liquid separator 640, a gas stream impinges ona tray and flows through the tray, as the liquid from the tray fall toan underflow 642. The vapor-liquid separator may further comprise ademister or chevron or other device located near the vapor outlet forpreventing liquid carry-over into the gas outlet from the vapor-liquidseparator 640.

Within the convection section 610, the temperature of the cracker streammay increase by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or300° C. and/or not more than about 650, 600, 575, 550, 525, 500, 475,450, 425, 400, 375, 350, 325, 300, or 275° C., so that the passing ofthe heated cracker stream exiting the convection section 610 through thevapor-liquid separator 640 may be performed at a temperature of least400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650° C. and/or notmore than 800, 775, 750, 725, 700, 675, 650, 625° C. When heaviercomponents are present, at least a portion or nearly all of the heavycomponents may be removed in the heavy fraction as an underflow 642. Atleast a portion of the light fraction 644 from the separator 640 may beintroduced into the cross-over section or the radiant zone tubes 624after the separation, alone or in combination with one or more othercracker streams, such as, for example, a predominantly C5-C22hydrocarbon stream or a C2-C4 hydrocarbon stream.

Referencing FIGS. 5 and 6, the cracker feed stream (either thenon-recycle cracker feed stream or when combined with the r-pyoil feedstream) 350 and 650 may be introduced into a furnace coil at or near theinlet of the convection section. The cracker feed stream may then passthrough at least a portion of the furnace coil in the convection section310 and 610, and dilution steam 360 and 660 may be added at some pointin order to control the temperature and cracking severity in the radiantsection 320 and 620. The amount of steam added may depend on the furnaceoperating conditions, including feed type and desired productdistribution, but can be added to achieve a steam-to-hydrocarbon ratioin the range of from 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75,or 0.4 to 0.6, calculated by weight. In an embodiment or in combinationwith any of the embodiments mentioned herein, the steam may be producedusing separate boiler feed water/steam tubes heated in the convectionsection of the same furnace (not shown in FIG. 5). Steam 360 and 660 maybe added to the cracker feed (or any intermediate cracker feed streamwithin the furnace) when the cracker feed stream has a vapor fraction of0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90 by weight, or in oneembodiment or in combination with any mentioned embodiments, by volume.

The heated cracker stream, which usually has a temperature of at least500, or at least 510, or at least 520, or at least 530, or at least 540,or at least 550, or at least 560, or at least 570, or at least 580, orat least 590, or at least 600, or at least 610, or at least 620, or atleast 630, or at least 640, or at least 650, or at least 660, or atleast 670, or at least 680, in each case ° C. and/or not more than 850,or not more than 840, or not more than 830, or not more than 820, or notmore than 810, or not more than 800, or not more than 790, or not morethan 780, or not more than 770, or not more than 760, or not more than750, or not more than 740, or not more than 730, or not more than 720,or not more than 710, or not more than 705, or not more than 700, or notmore than 695, or not more than 690, or not more than 685, or not morethan 680, or not more than 675, or not more than 670, or not more than665, or not more than 660, or not more than 655, or not more than 650,in each case ° C., or in the range of from 500 to 710° C., 620 to 740°C., 560 to 670° C., or 510 to 650° C., may then pass from the convectionsection 610 of the furnace to the radiant section 620 via the cross-oversection 630. In an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil containing feed stream 550 maybe added to the cracker stream at the cross-over section 530 as shown inFIG. 6. When introduced into the furnace in the cross-over section, ther-pyoil may be at least partially vaporized or atomized prior to beingcombined with the cracker stream at the cross-over. The temperature ofthe cracker stream passing through the cross-over 530 or 630 can be atleast 400, 425, 450, 475, or at least 500, or at least 510, or at least520, or at least 530, or at least 540, or at least 550, or at least 560,or at least 570, or at least 580, or at least 590, or at least 600, orat least 610, or at least 620, or at least 630, or at least 640, or atleast 650, or at least 660, or at least 670, or at least 680, in eachcase ° C. and/or not more than 850, or not more than 840, or not morethan 830, or not more than 820, or not more than 810, or not more than800, or not more than 790, or not more than 780, or not more than 770,or not more than 760, or not more than 750, or not more than 740, or notmore than 730, or not more than 720, or not more than 710, or not morethan 705, or not more than 700, or not more than 695, or not more than690, or not more than 685, or not more than 680, or not more than 675,or not more than 670, or not more than 665, or not more than 660, or notmore than 655, or not more than 650, in each case ° C., or in the rangeof from 620 to 740° C., 550 to 680° C., 510 to 630° C.

The resulting cracker feed stream then passes through the radiantsection, wherein the r-pyoil containing feed stream is thermally crackedto form lighter hydrocarbons, including olefins such as ethylene,propylene, and/or butadiene. The residence time of the cracker feedstream in the radiant section can be at least 0.1, or at least 0.15, orat least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or atleast 0.4, or at least 0.45, in each case seconds and/or not more than2, or not more than 1.75, or not more than 1.5, or not more than 1.25,or not more than 1, or not more than 0.9, or not more than 0.8, or notmore than 0.75, or not more than 0.7, or not more than 0.65, or not morethan 0.6, or not more than 0.5, in each case seconds. The temperature atthe inlet of the furnace coil is at least 500, or at least 510, or atleast 520, or at least 530, or at least 540, or at least 550, or atleast 560, or at least 570, or at least 580, or at least 590, or atleast 600, or at least 610, or at least 620, or at least 630, or atleast 640, or at least 650, or at least 660, or at least 670, or atleast 680, in each case ° C. and/or not more than 850, or not more than840, or not more than 830, or not more than 820, or not more than 810,or not more than 800, or not more than 790, or not more than 780, or notmore than 770, or not more than 760, or not more than 750, or not morethan 740, or not more than 730, or not more than 720, or not more than710, or not more than 705, or not more than 700, or not more than 695,or not more than 690, or not more than 685, or not more than 680, or notmore than 675, or not more than 670, or not more than 665, or not morethan 660, or not more than 655, or not more than 650, in each case ° C.,or in the range of from 550 to 710° C., 560 to 680° C., or 590 to 650°C., or 580 to 750° C., 620 to 720° C., or 650 to 710° C.

The coil outlet temperature can be at least 640, or at least 650, or atleast 660, or at least 670, or at least 680, or at least 690, or atleast 700, or at least 720, or at least 730, or at least 740, or atleast 750, or at least 760, or at least 770, or at least 780, or atleast 790, or at least 800, or at least 810, or at least 820, in eachcase ° C. and/or not more than 1000, or not more than 990, or not morethan 980, or not more than 970, or not more than 960, or not more than950, or not more than 940, or not more than 930, or not more than 920,or not more than 910, or not more than 900, or not more than 890, or notmore than 880, or not more than 875, or not more than 870, or not morethan 860, or not more than 850, or not more than 840, or not more than830, in each case ° C., in the range of from 730 to 900° C., 750 to 875°C., or 750 to 850° C.

The cracking performed in the coils of the furnace may include crackingthe cracker feed stream under a set of processing conditions thatinclude a target value for at least one operating parameter. Examples ofsuitable operating parameters include, but are not limited to maximumcracking temperature, average cracking temperature, average tube outlettemperature, maximum tube outlet temperature, and average residencetime. When the cracker stream further includes steam, the operatingparameters may include hydrocarbon molar flow rate and total molar flowrate. When two or more cracker streams pass through separate coils inthe furnace, one of the coils may be operated under a first set ofprocessing conditions and at least one of the other coils may beoperated under a second set or processing conditions. At least onetarget value for an operating parameter from the first set of processingconditions may differ from a target value for the same parameter in thesecond set of conditions by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5,1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, or 95 percent and/or not more than about 95, 90, 85, 80, 75, 70,65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 percent. Examples include0.01 to 30, 0.01 to 20, 0.01 to 15, 0.03 to 15 percent. The percentageis calculated according to the following formula:

[(measured value for operating parameter)−(target value for operatingparameter]/[(target value for operating parameter)], expressed as apercentage.

As used herein, the term “different,” means higher or lower.

The coil outlet temperature can be at least 640, 650, 660, 670, 680,690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820° C.and/or not more than 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910,900, 890, 880, 875, 870, 860, 850, 840, 830° C., in the range of from730 to 900° C., 760 to 875° C., or 780 to 850° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the addition of r-pyoil to a cracker feed stream may result inchanges to one or more of the above operating parameters, as compared tothe value of the operating parameter when an identical cracker feedstream is processed in the absence of r-pyoil. For example, the valuesof one or more of the above parameters may be at least 0.01, 0.03, 0.05,0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, or 95 percent different (e.g., higher or lower)than the value for the same parameter when processing an identical feedstream without r-pyoil, ceteris paribus. The percentage is calculatedaccording to the following formula:

[(measured value for operating parameter)−(target value for operatingparameter]/[(target value for operating parameter)], expressed as apercentage.

One example of an operating parameter that may be adjusted with theaddition of r-pyoil to a cracker stream is coil outlet temperature. Forexample, in an embodiment or in combination with any embodimentmentioned herein, the cracking furnace may be operated to achieve afirst coil outlet temperature (COT1) when a cracker stream having nor-pyoil is present. Next, r-pyoil may be added to the cracker stream,via any of the methods mentioned herein, and the combined stream may becracked to achieve a second coil outlet temperature (COT2) that isdifferent than COT1.

In some cases, when the r-pyoil is heavier than the cracker stream, COT2may be less than COT1, while, in other case, when the r-pyoil is lighterthan the cracker stream, COT2 may be greater than or equal to COT1. Whenthe r-pyoil is lighter than the cracker stream, it may have a 50%boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50and/or not more than 80, 75, 70, 65, 60, 55, or 50 percent higher thanthe 50% boiling point of the cracker stream. The percentage iscalculated according to the following formula:

[(50% boiling point of r-pyoil in ° R)−(50% boiling point of crackerstream)]/[(50% boiling point of cracker stream)], expressed as apercentage.

Alternatively, or in addition, the 50% boiling point of the r-pyoil maybe at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, 90, 95, or 100° C. and/or not more than 300, 275, 250, 225, or200° C. lower than the 50% boiling point of the cracker stream. Heaviercracker streams can include, for example, vacuum gas oil (VGO),atmospheric gas oil (AGO), or even coker gas oil (CGO), or combinationsthereof.

When the r-pyoil is lighter than the cracker stream, it may have a 50%boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50and/or not more than 80, 75, 70, 65, 60, 55, or 50 percent lower thanthe 50% boiling point of the cracker stream. The percentage iscalculated according to the following formula:

[(50% boiling point of r-pyoil)−(50% boiling point of crackerstream)]/[(50% boiling point of cracker stream)], expressed as apercentage.

Additionally, or in the alternative, the 50% boiling point of ther-pyoil may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, 95, or 100° C. and/or not more than 300, 275,250, 225, or 200° C. higher than the 50% boiling point of the crackerstream. Lighter cracker streams can include, for example, LPG, naphtha,kerosene, natural gasoline, straight run gasoline, and combinationsthereof.

In some cases, COT1 can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45,50° C. and/or not more than about not more than 150, 140, 130, 125, 120,110, 105, 100, 90, 80, 75, 70, or 65° C. different (higher or lower)than COT2, or COT1 can be at least 0.3, 0.6, 1, 2, 5, 10, 15, 20, or 25and/or not more than 80, 75, 70, 65, 60, 50, 45, or 40 percent differentthan COT2 (with the percentage here defined as the difference betweenCOT1 and COT2 divided by COT1, expressed as a percentage). At least oneor both of COT1 and COT2 can be at least 730, 750, 77, 800, 825, 840,850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980,990 and/or not more than 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100,1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980,970, 960 950, 940, 930, 920, 910, or 900° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the mass velocity of the cracker feed stream through at leastone, or at least two radiant coils (for clarity as determine across theentire coil as opposed to a tube within a coil) is in the range of 60 to165 kilograms per second (kg/s) per square meter (m2) of cross-sectionalarea (kg/s/m2), 60 to 130 (kg/s/m2), 60 to 110 (kg/s/m2), 70 to 110(kg/s/m2), or 80 to 100 (kg/s/m2). When steam is present, the massvelocity is based on the total flow of hydrocarbon and steam.

In one embodiment or in combination with any mentioned embodiments,there is provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first coil        outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        at a second coil outlet temperature (COT2), wherein said second        coil outlet temperature is lower, or at least 3° C. lower, or at        least 5° C. lower than said first coil outlet temperature.

The reason or cause for the temperature drop in the second coil outlettemperature (COT2) is not limited, provided that COT2 is lower than thefirst coil outlet temperature (COT1). In one embodiment or incombination with any mentioned embodiments, In one embodiment or incombination with any other mentioned embodiments, the COT2 temperatureon the r-pyoil fed coils can be set to a temperature that lower than, orat least 1, 2, 3, 4, or at least 5° C. lower than COT1 (“Set” Mode), orit can be allowed to change or float without setting the temperature onthe r-pyoil fed coils (“Free Float” Mode”).

The COT2 can be set at least 5° C. lower than COT1 in a Set Mode. Allcoils in a furnace can be r-pyoil containing feed streams, or at least1, or at least two of the coils can be r-pyoil containing feed streams.In either case, at least one of the r-pyoil containing coils can be in aSet Mode. By reducing the cracking severity of the combined crackingstream, one can take advantage of the lower heat energy required tocrack r-pyoil when it has an average number average molecular weightthat is higher than the cracker feed stream, such as a gaseous C2-C4feed. While the cracking severity on the cracker feed (e.g. C2-C4) canbe reduced and thereby increase the amount of unconverted C2-C4 feed ina single pass, the higher amount of unconverted feed (e.g. C2-C4 feed)is desirable to increase the ultimate yield of olefins such as ethyleneand/or propylene through multiple passes by recycling the unconvertedC2-C4 feed through the furnace. Optionally, other cracker products, suchas the aromatic and diene content, can be reduced.

In one embodiment or in combination with any mentioned embodiments, theCOT2 in a coil can be fixed in a Set Mode to be lower than, or at least1, 2, 3, 4, or at least 5° C. lower than the COT1 when the hydrocarbonmass flow rate of the combined cracker stream in at least one coil isthe same as or less than the hydrocarbon mass flow rate of the crackerstream in step (a) in said coil. The hydrocarbon mass flow rate includesall hydrocarbons (cracker feed and if present the r-pyoil and/or naturalgasoline or any other types of hydrocarbons) and other than steam.Fixing the COT2 is advantageous when the hydrocarbon mass flow rate ofthe combined cracker stream in step (b) is the same as or less than thehydrocarbon mass flow rate of the cracker stream in step (a) and thepyoil has a higher average molecular weight than the average molecularweight of the cracker stream. At the same hydrocarbon mass flow rates,when pyoil has a heavier average molecular weight than the crackerstream, the COT2 will tend to rise with the addition of pyoil becausethe higher molecular weight molecules require less thermal energy tocrack. If one desires to avoid overcracking the pyoil, the lowered COT2temperature can assist to reduce by-product formation, and while theolefin yield in the singe pass is also reduced, the ultimate yield ofolefins can be satisfactory or increased by recycling unconvertedcracker feed through the furnace.

In a Set Mode, the temperature can be fixed or set by adjusting thefurnace fuel rate to burners.

In one embodiment or in combination with any other mentionedembodiments, the COT2 is in a Free Float Mode and is as a result offeeding pyoil and allowing the COT2 to rise or fall without fixing atemperature to the pyoil fed coils. In this embodiment, not all of thecoils contain r-pyoil. The heat energy supplied to the r-pyoilcontaining coils can be supplied by keeping constant temperature on, orfuel feed rate to the burners on the non-recycle cracker feed containingcoils. Without fixing or setting the COT2, the COT2 can be lower thanCOT1 when pyoil is fed to the cracker stream to form a combined crackerstream that has a higher hydrocarbon mass flow rate than the hydrocarbonmass flow rate of the cracker stream in step (a). Pyoil added to acracker feed to increase the hydrocarbon mass flow rate of the combinedcracker feed lowers the COT2 and can outweigh the temperature riseeffect of using a higher average molecular weight pyoil. These effectscan be seen while other cracker conditions are held constant, such asthe dilution steam ratio, feed locations, composition of the crackerfeed and pyoil, and fuel feed rates to the firebox burners in thefurnace on the tubes containing only cracker feed and no feed ofr-pyoil.

The COT2 can be lower than, or at least 1, 2, 3, 4, 5, 8, 10, 12, 15,18, 20, 25, 30, 35, 40, 45, 50° C. and/or not more than about not morethan 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65° C.lower than COT1.

Independent of the reason or cause of the temperature drop in COT2, thetime period for engaging step (a) is flexible, but ideally, step (a)reaches a steady state before engaging step (b). In one embodiment or incombination with any mentioned embodiments, step (a) is in operation forat least 1 week, or at least 2 weeks, or at least 1 month, or at least 3months, or at least 6 months, or at least 1 year, or at least 1.5 years,or at least 2 years. The step (a) can be represented by a crackerfurnace in operation that has never accepted a feed of pyoil or acombined feed of cracker feed and pyoil. Step (b) can be the first timea furnace has accepted a feed of pyoil or a combined cracker feedcontaining pyoil. In one embodiment or in combination with any othermentioned embodiments, steps (a) and (b) can be cycled multiple timesper year, such as at least 2×/yr, or at least 3×/yr, or at least 4×/yr,or at least 5×/yr, or at least 6×/yr, or at least 8×/yr, or at least12×/yr, as measured on a calendar year. Campaigning a feed of pyoil isrepresentative of multiple cycling of steps (a) and (b). When the feedsupply of pyoil is exhausted or shut off, the COT1 is allowed to reach asteady state temperature before engaging step (b).

Alternatively, the feed of pyoil to a cracker feed can be continuousover the entire course of at least 1 calendar year, or at least 2calendar years.

In one embodiment or in combination with any other mentionedembodiments, the cracker feed composition used in steps (a) and (b)remains unchanged, allowing for regular compositional variationsobserved during the course of a calendar year. In one embodiment or incombination with any other mentioned embodiments, the flow of crackerfeed in step (a) is continuous and remains continuous as pyoil is to thecracker feed to make a combined cracker feed. The cracker feed in steps(a) and (b) can be drawn from the same source, such as the sameinventory or pipeline.

In one embodiment or in combination with any mentioned embodiments, theCOT2 is lower than, or at least 1, 2, 3, 4, or at least 5° C. lower forat least 30% of the time that the pyoil is fed to the cracker stream toform the combined cracker stream, or at least 40% of the time, or atleast 50% of the time, or at least 60% of the time, or at least 70% ofthe time, or at least 80% of the time, or at least 85% of the time, orat least 90% of the time, or at least 95% of the time, the time measuredas when all conditions, other than COT's, are held constant, such ascracker and pyoil feed rates, steam ratio, feed locations, compositionof the cracker feed and pyoil, etc.

In one embodiment or in combination with any mentioned embodiments, thehydrocarbon mass flow rate of combined cracker feed can be increased.There is now provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first        hydrocarbon mass flow rate (MF1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream having a second        hydrocarbon mass flow rate (MF2) that is higher than MF1; and    -   (c) cracking said combined cracker stream at MF2 in said        cracking unit to obtain an olefin-containing effluent that has a        combined output of ethylene and propylene that same as or higher        than the output of ethylene and propylene obtained by cracking        only said cracker stream at MF1.

The output refers to the production of the target compounds in weightper unit time, for example, kg/hr. Increasing the mass flow rate of thecracker stream by addition of r-pyoil can increase the output ofcombined ethylene and propylene, thereby increasing the throughput ofthe furnace. Without being bound to a theory, it is believed that thisis made possible because the total energy of reaction is not asendothermic with the addition of pyoil relative to total energy ofreaction with a lighter cracker feed such as propane or ethane. Sincethe heat flux on the furnace is limited and the total heat of reactionof pyoil is less endothermic, more of the limited heat energy becomesavailable to continue cracking the heavy feed per unit time. The MF2 canbe increased by at least 1, 2, 3, 4, 5, 7, 10, 10, 13, 15, 18, or 20%through a r-pyoil fed coil, or can be increased by at least 1, 2, 3, 5,7, 10, 10, 13, 15, 18, or 20% as measured by the furnace output providedthat at least one coil processes r-pyoil. Optionally, the increase incombined output of ethylene and propylene can be accomplished withoutvarying the heat flux in the furnace, or without varying the r-pyoil fedcoil outlet temperature, or without varying the fuel feed rate to theburners assigned to heat the coils containing only non-recycle contentcracker feed, or without varying the fuel feed rate to any of theburners in the furnace. The MF2 higher hydrocarbon mass flow rate in ther-pyoil containing coils can be through one or at least one coil in afurnace, or two or at least two, or 50% or at least 50%, or 75% or atleast 75%, or through all of the coils in a furnace.

The olefin-containing effluent stream can have a total output ofpropylene and ethylene from the combined cracker stream at MF2 that isthe same as or higher than the output of propylene and ethylene of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{{Omf}2} - {{Omf}1}}{{Omf}1} \times 100}$

-   -   where O_(mf1) is the combined output of propylene and ethylene        content in the cracker effluent at MF1 made without r-pyoil; and    -   O_(mf2) is the combined output of propylene and ethylene content        in the cracker effluent at MF2 made with r-pyoil.

The olefin-containing effluent stream can have a total output ofpropylene and ethylene from the combined cracker stream at MF2 that isleast 1, 5, 10, 15, 20%, and/or up to 80, 70, 65% of the mass flow rateincrease between MF2 and MF1 on a percentage basis. Examples of suitableranges include 1 to 80, or 1 to 70, or 1 to 65, or 5 to 80, or 5 to 70,or 5 to 65, or 10 to 80, or 10 to 70, or 10 to 65, or 15 to 80, or 15 to70, or 15 to 65, or 20 to 80, or 20 to 70, or 20 to 65, or 25 to 80, or25 to 70, or 26 to 65, or 35 to 80, or 35 to 70, or 35 to 65, or 40 to80, or 40 to 70, or 40 to 65, each expressed as a percent %. Forexample, if the percentage difference between MF2 and MF1 is 5%, and thetotal output of propylene and ethylene is increased by 2.5%, the olefinincrease as a function of mass flow increase is 50% (2.5%/5%×100). Thiscan be determined as:

${\%{relative}{increase}} = {\frac{\Delta O\%}{\Delta{MF}\%} \times 100}$

-   -   where ΔO % is percentage increase between the combined output of        propylene and ethylene content in the cracker effluent at MF1        made without r-pyoil and MF2 made with r-pyoil (using the        aforementioned equation); and    -   ΔMF % is the percentage increase of MF2 over MF1.

Optionally, the olefin-containing effluent stream can have a total wt. %of propylene and ethylene from the combined cracker stream at MF2 thatis the same as or higher than the wt. % of propylene and ethylene of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{{Emf}2} - {{Emf}1}}{{Emf}1} \times 100}$

-   -   where E_(mf1) is the combined wt. % of propylene and ethylene        content in the cracker effluent at MF1 made without r-pyoil; and    -   E_(mf2) is the combined wt. % of propylene and ethylene content        in the cracker effluent at MF2 made with r-pyoil.

There is also provided a method for making one or more olefins, saidmethod comprising:

-   -   (a) cracking a cracker stream in a cracking furnace to provide a        first olefin-containing effluent exiting the cracking furnace at        a first coil outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        to provide a second olefin-containing effluent exiting the        cracking furnace at a second coil outlet temperature (COT2),        wherein, when said r-pyoil is heavier than said cracker stream,        COT2 is equal to or less than COT1,    -   wherein, when said r-pyoil is lighter than said cracker stream,        COT2 is greater than or equal to COT1.

In this method, the embodiments described above for a COT2 lower thanCOT1 are also applicable here. The COT2 can be in a Set Mode or FreeFloat Mode. In one embodiment or in combination with any other mentionedembodiments, the COT2 is in a Free Float Mode and the hydrocarbon massflow rate of the combined cracker stream in step (b) is higher than thehydrocarbon mass flow rate of the cracker stream in step (a). In oneembodiment or in combination with any mentioned embodiments, the COT2 isin a Set Mode.

In one embodiment or in combination with any mentioned embodiments,there is provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first coil        outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        at a second coil outlet temperature (COT2), wherein said second        coil outlet temperature is higher than the first coil outlet        temperature.

The COT2 can be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45,50° C. and/or not more than about not more than 150, 140, 130, 125, 120,110, 105, 100, 90, 80, 75, 70, or 65° C. higher than COT1.

In one embodiment or in combination with any other mentionedembodiments, r-pyoil is added to the inlet of at least one coil, or atleast two coils, or at least 50%, or at least 75%, or all of the coils,to form at least one combined cracker stream, or at least two combinedcracker streams, or at least the same number of combined crackersstreams as coils accepting a feed of r-pyoil. At least one, or at leasttwo of the combined cracker streams, or at least all of the r-pyoil fedcoils can have a COT2 that is higher than their respective COT1. In oneembodiment or in combination with any mentioned embodiments, at leastone, or at least two coils, or at least 50%, or at least 75% of thecoils within said cracking furnace contain only non-recycle contentcracker feed, with at least one of the coils in the cracking furnacebeing fed with r-pyoil, and the coil or at least some of multiple coilsfed with r-pyoil having a COT2 higher than their respective COT1.

In one embodiment or in combination with any mentioned embodiments, thehydrocarbon mass flow rate of the combined stream in step (b) issubstantially the same as or lower than the hydrocarbon mass flow rateof the cracker stream in step (a). By substantially the same is meantnot more than a 2% difference, or not more than a 1% difference, or notmore than a 0.25% difference. When the hydrocarbon mass flow rate of thecombined cracker stream in step (b) is substantially the same as orlower than the hydrocarbon mass flow rate of the cracker stream (a), andthe COT2 is allowed to operate in a Free Float Mode (where at least 1 ofthe tubes contains non-recycle content cracker stream), the COT2 on ther-pyoil containing coil can rise relative to COT1. This is the case eventhough the pyoil, having a larger number average molecular weightcompared to the cracker stream, requires less energy to crack. Withoutbeing bound to a theory, it is believed that one or a combination offactors contribute to the temperature rise, including the following:

(i) Lower heat energy is required to crack pyoil in the combined stream.

(ii) The occurrence of exothermic reactions among cracked products ofpyoil, such as diels-alder reactions.

This effect can be seen when the other process variables are constant,such as the firebox fuel rate, dilution steam ratio, location of feeds,and composition of the cracker feed.

In one embodiment or in combination with any mentioned embodiments, theCOT2 can be set or fixed to a higher temperature than COT1 (the SetMode). This is more applicable when the hydrocarbon mass flow rate ofthe combined cracker stream is higher than the hydrocarbon mass flowrate of the cracker stream which would otherwise lower the COT2. Thehigher second coil outlet temperature (COT2) can contribute to anincreased severity and a decreased output of unconverted lighter crackerfeed (e.g. C2-C4 feed), which can assist with downstream capacityrestricted fractionation columns.

In one embodiment or in combination with any mentioned embodiments,whether the COT2 is higher or lower than COT1, the cracker feedcompositions are the same when a comparison is made between COT2 with aCOT1. Desirably, the cracker feed composition in step (a) is the samecracker composition as used to make the combined cracker stream in step(b). Optionally, the cracker composition feed in step (a) iscontinuously fed to the cracker unit, and the addition of pyoil in step(b) is to the continuous cracker feed in step (a). Optionally, the feedof pyoil to the cracker feed is continuous for at least 1 day, or atleast 2 days, or at least 3 days, or at least 1 week, or at least 2weeks, or at least 1 month, or at least 3 months, or at least 6 monthsor at least 1 year.

The amount of raising or lowering the cracker feed in step (b) in any ofthe mentioned embodiments can be at least 2%, or at least 5%, or atleast 8%, or at least 10%. In one embodiment or in combination with anymentioned embodiments, the amount of lowering the cracker feed in step(b) can be an amount that corresponds to the addition of pyoil byweight. In one embodiment or in combination with any mentionedembodiments, the mass flow of the combined cracker feed is at least 1%,or at least 5%, or at least 8%, or at least 10% higher than thehydrocarbon mass flow rate of the cracker feed in step (a).

In any or all of the mentioned embodiments, the cracker feed or combinedcracker feed mass flows and COT relationships and measurements aresatisfied if any one coil in the furnace satisfies the statedrelationships but can also be present in multiple tubes depending on howthe pyoil is fed and distributed.

In an embodiment or in combination with any of the embodiments mentionedherein, the burners in the radiant zone provide an average heat fluxinto the coil in the range of from 60 to 160 kW/m2 or 70 to 145 kW/m2 or75 to 130 kW/m2. The maximum (hottest) coil surface temperature is inthe range of 1035 to 1150° C. or 1060 to 1180° C. The pressure at theinlet of the furnace coil in the radiant section is in the range of 1.5to 8 bar absolute (bara), or 2.5 to 7 bara, while the outlet pressure ofthe furnace coil in the radiant section is in the range of from 1.03 to2.75 bara, or 1.03 to 2.06 bara. The pressure drop across the furnacecoil in the radiant section can be from 1.5 to 5 bara, or 1.75 to 3.5bara, or 1.5 to 3 bara, or 1.5 to 3.5 bara.

In an embodiment or in combination with any of the embodiments mentionedherein, the yield of olefin-ethylene, propylene, butadiene, orcombinations thereof—can be at least 15, or at least 20, or at least 25,or at least 30, or at least 35, or at least 40, or at least 45, or atleast 50, or at least 55, or at least 60, or at least 65, or at least70, or at least 75, or at least 80, in each case percent. As usedherein, the term “yield” refers to the mass of product/mass offeedstock×100%. The olefin-containing effluent stream comprises at leastabout 30, or at least 40, or at least 50, or at least 60, or at least70, or at least 75, or at least 80, or at least 85, or at least 90, orat least 95, or at least 97, or at least 99, in each case weight percentof ethylene, propylene, or ethylene and propylene, based on the totalweight of the effluent stream.

In an embodiment or in combination with one or more embodimentsmentioned herein, the olefin-containing effluent stream 670 can compriseC2 to C4 olefins, or propylene, or ethylene, or C4 olefins, in an amountof at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, or 90 weight percent, based on the weight of theolefin-containing effluent. The stream may comprise predominantlyethylene, predominantly propylene, or predominantly ethylene andpropylene, based on the olefins in the olefin-containing effluent, orbased on the weight of the C1-C5 hydrocarbons in the olefin-containingeffluent, or based on the weight of the olefin-containing effluentstream. The weight ratio of ethylene-to-propylene in theolefin-containing effluent stream can be at least about 0.2:1, 0.3:1,0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1,1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1 and/or not more than3:1, 2.9:1, 2.8:1, 2.7:1, 2.5:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.7:1, 1.5:1,or 1.25:1. In an embodiment or in combination with one or moreembodiments mentioned herein, the olefin-containing effluent stream canhave a ratio of propylene:ethylene that is higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil at equivalent dilution steamratios, feed locations, cracker feed compositions (other than ther-pyoil), and allowing the coils fed with r-pyoil to be in the FloatMode, or if all coils in a furnace are fed with r-pyoil, then at thesame temperature prior to feeding r-pyoil. As discussed above, this ispossible when the mass flow of the cracker feed remains substantiallythe same resulting in a higher hydrocarbon mass flow rate of thecombined cracker stream when r-pyoil is added relative to the originalfeed of the cracker stream.

The olefin-containing effluent stream can have a ratio ofpropylene:ethylene that is at least 1% higher, or at least 2% higher, orat least 3% higher, or at least 4% higher, or at least 5% higher or atleast 7% higher or at least 10% higher or at least 12% higher or atleast 15% higher or at least 17% higher or at least 20% higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil. Alternatively or in addition, theolefin-containing effluent stream can have a ratio of propylene:ethylenethat is up to 50% higher, or up to 45% higher, or up to 40% higher, orup to 35% higher, or up to 25% higher, or up to 20% higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil, in each case determined as:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the propylene:ethylene ratio by wt. % in the cracker        effluent made without r-pyoil; and    -   E_(r) is the propylene:ethylene ratio by wt. % in the cracker        effluent made with r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the amount of ethylene and propylene can remain substantiallyunchanged or increased in the cracked olefin-containing effluent streamrelative to an effluent stream without r-pyoil. It is surprising that aliquid r-pyoil can be fed to a gas fed furnace that accepts and cracks apredominant C2-C4 composition and obtain an olefin-containing effluentstream that can remain substantially unchanged or improved in certaincases relative to a C2-C4 cracker feed without r-pyoil. The heavymolecular weight of r-pyoil could have predominately contributed to theformation of aromatics and participate in the formation of olefins(ethylene and propylene in particular) in only a minor amount. However,we have found that the combined weight percent of ethylene andpropylene, and even the output, does not significantly drop, and in manycases stays the same or can increase when r-pyoil is added to a crackerfeed to form a combined cracker feed at the same hydrocarbon mass flowrates relative to a cracker feed without r-pyoil. The olefin-containingeffluent stream can have a total wt. % of propylene and ethylene that isthe same as or higher than the propylene and ethylene content of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the combined wt. % of propylene and ethylene content        in the cracker effluent made without r-pyoil; and    -   E_(r) is the combined wt. % of propylene and ethylene content in        the cracker effluent made with r-pyoil.

In an embodiment or in combination with one or more embodimentsmentioned herein, the wt. % of propylene can improve in anolefin-containing effluent stream when the dilution steam ratio (ratioof steam:hydrocarbons by weight) is above 0.3, or above 0.35, or atleast 0.4. The increase in the wt. % of propylene when the dilutionsteam ratio is at least 0.3, or at least 0.35, or at least 0.4 can be upto 0.25 wt. %, or up to 0.4 wt. %, or up to 0.5 wt. %, or up to 0.7 wt.%, or up to 1 wt. %, or up to 1.5 wt. %, or up to 2 wt. %, where theincrease is measured as the simple difference between the wt. % ofpropylene between an olefin-containing effluent stream made with r-pyoilat a dilution steam ratio of 0.2 and an olefin-containing effluentstream made with r-pyoil at a dilution steam ratio of at least 0.3, allother conditions being the same.

When the dilution steam ratio is increased as noted above, the ratio ofpropylene:ethylene can also increase, or can be at least 1% higher, orat least 2% higher, or at least 3% higher, or at least 4% higher, or atleast 5% higher or at least 7% higher or at least 10% higher or at least12% higher or at least 15% higher or at least 17% higher or at least 20%higher than the propylene:ethylene ratio of an olefin-containingeffluent stream made with r-pyoil at a dilution steam ratio of 0.2.

In an embodiment or in combination with one or more embodimentsmentioned herein, when the dilution steam ratio is increased, theolefin-containing effluent stream can have a reduced wt. % of methane,when measured relative to an olefin-containing effluent stream at adilution steam ratio of 0.2. The wt. % of methane in theolefin-containing effluent stream can be reduced by at least 0.25 wt. %,or by at least 0.5 wt. %, or by at least 0.75 wt. %, or by at least 1wt. %, or by at least 1.25 wt. %, or by at least 1.5 wt. %, measured asthe absolute value difference in wt. % between the olefin-containingeffluent stream at a dilution steam ratio of 0.2 and at the higherdilution steam ratio value.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of unconverted products in theolefin-containing effluent is decreased, when measured relative to acracker feed that does not contain r-pyoil and all other conditionsbeing the same, including hydrocarbon mass flow rate. For example, theamount of propane and/or ethane can be decreased by addition of r-pyoil.This can be advantageous to decrease the mass flow of the recycle loopto thereby (a) decrease cryogenic energy costs and/or (b) potentiallyincrease capacity on the plant if the plant is already capacityconstrained. Further it can debottleneck the propylene fractionator ifit is already to its capacity limit. The amount of unconverted productsin the olefin containing effluent can decrease by at least 2%, or atleast 5%, or at least 8%, or at least 10%, or at least 13%, or at least15%, or at least 18%, or at least 20%.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of unconverted products (e.g. combinedpropane and ethane amount) in the olefin-containing effluent isdecreased while the combined output of ethylene and propylene does notdrop and is even improved, when measured relative to a cracker feed thatdoes not contain r-pyoil. Optionally, all other conditions are the sameincluding the hydrocarbon mass flow rate and with respect totemperature, where the fuel feed rate to heat the burners to thenon-recycle content cracker fed coils remains unchanged, or optionallywhen the fuel feed rate to all coils in the furnace remains unchanged.Alternatively, the same relationship can hold true on a wt. % basisrather than an output basis.

For example, the combined amount (either or both of output or wt. %) ofpropane and ethane in the olefin containing effluent can decrease by atleast 2%, or at least 5%, or at least 8%, or at least 10%, or at least13,%, or at least 15%, or at least 18%, or at least 20%, and in eachcase up to 40% or up to 35% or up to 30%, in each case without adecrease in the combined amount of ethylene and propylene, and even canaccompany an increase in the combined amount of ethylene and propylene.In another example, the amount of propane in the olefin containingeffluent can decrease by at least 2%, or at least 5%, or at least 8%, orat least 10%, or at least 13,%, or at least 15%, or at least 18%, or atleast 20%, and in each case up to 40% or up to 35% or up to 30%, in eachcase without a decrease in the combined amount of ethylene andpropylene, and even can accompany an increase in the combined amount ofethylene and propylene. In any one of these embodiments, the crackerfeed (other than r-pyoil and as fed to the inlet of the convection zone)can be predominately propane by moles, or at least 90 mole % propane, orat least 95 mole % propane, or at least 96 mole % propane, or at least98 mole % propane; or the fresh supply of cracker feed can be at leastHD5 quality propane.

In an embodiment or in combination with one or more embodimentsmentioned herein, the ratio of propane:(ethylene and propylene) in theolefin-containing effluent can decrease with the addition of r-pyoil tothe cracker feed when measured relative to the same cracker feed withoutpyoil and all other conditions being the same, measured either as wt. %or output. The ratio of propane:(ethylene and propylene combined) in theolefin-containing effluent can be not more than 0.50:1, or less than0.50:1, or not more than 0.48:1, or not more than 0.46:1, or no morethan 0.43:1, or no more than 0.40:1, or no more than 0.38:1, or no morethan 0.35:1, or no more than 0.33:1, or no more than 0.30:1. The lowratios indicate that a high amount of ethylene+propylene can be achievedor maintained with a corresponding drop in unconverted products such aspropane.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of C6+ products in the olefin-containingeffluent can be increased, if such products are desired such as for aBTX stream to make derivates thereof, when r-pyoil and steam are feddownstream of the inlet to the convection box, or when one or both ofr-pyoil and steam are fed at the cross-over location. The amount of C6+products in the olefin-containing effluent can be increased by 5%, or by10%, or by 15%, or by 20%, or by 30% when r-pyoil and steam are feddownstream of the inlet to the convection box, when measured againstfeeding r-pyoil at the inlet to the convection box, all other conditionsbeing the same. The % increase can be calculated as:

${\%{increase}} = {\frac{{Ei} - {Ed}}{Ei} \times 100}$

-   -   where E_(i) is the C₆₊ content in the olefin-containing cracker        effluent made by introducing r-pyoil at the inlet of the        convection box; and    -   E_(d) is the C₆₊ content in the olefin-containing cracker        effluent made by introducing r-pyoil and steam downstream of the        inlet of the convection box.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracked olefin-containing effluent stream may includerelatively minor amounts of aromatics and other heavy components. Forexample, the olefin-containing effluent stream may include at least 0.5,1, 2, or 2.5 weight percent and/or not more than about 20, 19, 18, 17,16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 weight percentof aromatics, based on the total weight of the stream. We have foundthat the level of C6+ species in the olefin-containing effluent can benot more than 5 wt. %, or not more than 4 wt. %, or not more than 3.5wt. %, or not more than 3 wt. %, or not more than 2.8 wt. %, or not morethan 2.5 wt. %. The C6+ species includes all aromatics, as well as allparaffins and cyclic compounds having a carbon number of 6 or more. Asused throughout, the mention of amounts of aromatics can be representedby amounts of C6+ species since the amount of aromatics would not exceedthe amount of C6+ species.

The olefin-containing effluent may have an olefin-to-aromatic ratio, byweight %, of at least 2:1, 3.1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1,23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, or 30:1 and/or not more than100:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1,35:1, 30:1, 25:1, 20:1, 15:1, 10:1, or 5:1. As used herein,“olefin-to-aromatic ratio” is the ratio of total weight of C2 and C3olefins to the total weight of aromatics, as defined previously. In anembodiment or in combination with any of the embodiments mentionedherein, the effluent stream can have an olefin-to-aromatic ratio of atleast 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1,10.5:1, 11.5:1, 12.5:1, or 13:5:1.

The olefin-containing effluent may have an olefin:C6+ ratio, by weight%, of at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or atleast 17:1, or at least 19:1, or at least 20:1, or at least 25:1, orleast 28:1, or at least 30:1. In addition or in the alternative, theolefin-containing effluent may have an olefin:C6+ ratio of up to 40:1,or up to 35:1, or up to 30:1, or up to 25:1, or up to 23:1. As usedherein, “olefin-to-aromatic ratio” is the ratio of total weight of C2and C3 olefins to the total weight of aromatics, as defined previously.

Additionally, or in the alternative, the olefin-containing effluentstream can have an olefin-to-C6+ ratio of at least about 1.5:1, 1.75:1,2:1, 2.25:1, 2.5:1, 2.75:1, 3:1, 3.25:1, 3.5:1, 3.75:1, 4:1, 4.25:1,4.5:1, 4.75:1, 5:1, 5.25:1, 5.5:1, 5.75:1, 6:1, 6.25:1, 6.5:1, 6.75:1,7:1, 7.25:1, 7.5:1, 7.75:1, 8:1, 8.25:1, 8.5:1, 8.75:1, 9:1, 9.5:1,10:1, 10.5:1, 12:1, 13:1, 15:1, 17:1, 19:1, 20:1, 25:1, 28:1, or 30:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin:aromatic ratio decreases with an increase in theamount of r-pyoil added to the cracker feed. Since r-pyoil cracks at alower temperature, it will crack earlier than propane or ethane, andtherefore has more time to react to make other products such asaromatics. Although the aromatic content in the olefin-containingeffluent increases with an increasing amount of pyoil, the amount ofaromatics produced is remarkably low as noted above.

The olefin-containing composition may also include trace amounts ofaromatics. For example, the composition may have a benzene content of atleast 0.25, 0.3, 0.4, 0.5 weight percent and/or not more than about 2,1.7, 1.6, 1.5 weight percent. Additionally, or in the alternative, thecomposition may have a toluene content of at least 0.005, 0.010, 0.015,or 0.020 and/or not more than 0.5, 0.4, 0.3, or 0.2 weight percent. Bothpercentages are based on the total weight of the composition.Alternatively, or in addition, the effluent can have a benzene contentof at least 0.2, 0.3, 0.4, 0.5, or 0.55 and/or not more than about 2,1.9, 1.8, 1.7, or 1.6 weight percent and/or a toluene content of atleast 0.01, 0.05, or 0.10 and/or not more than 0.5, 0.4, 0.3, or 0.2weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent withdrawn from a cracking furnacewhich has cracked a composition comprising r-pyoil may include anelevated amount of one or more compounds or by-products not found inolefin-containing effluent streams formed by processing conventionalcracker feed. For example, the cracker effluent formed by crackingr-pyoil (r-olefin) may include elevated amounts of 1,3-butadiene,1,3-cyclopentadiene, dicyclopentadiene, or a combination of thesecomponents. In an embodiment or in combination with any of theembodiments mentioned herein, the total amount (by weight) of thesecomponents may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, or 85 percent higher than an identical cracker feedstream processed under the same conditions and at the same mass feedrate, but without r-pyoil. The total amount (by weight) of 1,3-butadienemay be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, or 85 percent higher than an identical cracker feed streamprocessed under the same conditions and at the same mass feed rate, butwithout r-pyoil. The total amount (by weight) of 1,3-cyclopentadiene maybe at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, or 85 percent higher than an identical cracker feed stream processedunder the same conditions and at the same mass feed rate, but withoutr-pyoil. The total amount (by weight) of dicyclopentadiene may be atleast 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or85 percent higher than an identical cracker feed stream processed underthe same conditions and at the same mass feed rate, but without r-pyoil.The percent difference is calculated by dividing the difference inweight percent of one or more of the above components in the r-pyoil andconventional streams by the amount (in weight percent) of the componentin the conventional stream, or:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the wt. % of the component in the cracker effluent        made without r-pyoil; and    -   E_(r) is the wt. % of the component in the cracker effluent made        with r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise acetylene.The amount of acetylene can be at least 2000 ppm, at least 5000 ppm, atleast 8000 ppm, or at least 10,000 ppm based on the total weight of theeffluent stream from the furnace. It may also be not more than 50,000ppm, not more than 40,000 ppm, not more than 30,000 ppm, or not morethan 25,000 ppm, or not more than 10,000 ppm, or not more than 6,000ppm, or not more than 5000 ppm.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise methylacetylene and propadiene (MAPD). The amount of MAPD may be at least 2ppm, at least 5 ppm, at least 10 ppm, at least 20 pm, at least 50 ppm,at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000ppm, or at least 10,000 ppm, based on the total weight of the effluentstream. It may also be not more than 50,000 ppm, not more than 40,000ppm, or not more than 30,000 ppm, or not more than 10,000 ppm, or notmore than 6,000 ppm, or not more than 5,000 ppm.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise low or noamounts of carbon dioxide. The olefin-containing effluent stream canhave an amount, in wt. %, of carbon dioxide that is not more than theamount of carbon dioxide in an effluent stream obtained by cracking thesame cracker feed but without r-pyoil at equivalent conditions, or anamount this is not higher than 5%, or not higher than 2% of the amountof carbon dioxide, in wt. %, or the same amount as a comparativeeffluent stream without r-pyoil. Alternatively or in addition, theolefin-containing effluent stream can have an amount of carbon dioxidethat is not more than 1000 ppm, or not more than 500 ppm, or not morethan 100 ppm, or not more than 80 ppm, or not more than 50 ppm, or notmore than 25 ppm, or not more than 10 ppm, or not more than 5 ppm.

Turning now to FIG. 9, a block diagram illustrating the main elements ofthe furnace effluent treatment section are shown.

As shown in FIG. 9, the olefin-containing effluent stream from thecracking furnace 700, which includes recycle content) is cooled rapidly(e.g., quenched) in a transfer line exchange (“TLE”) 680 as shown inFIG. 8 in order to prevent production of large amounts of undesirableby-products and to minimize fouling in downstream equipment, and also togenerate steam. In an embodiment or in combination with any of theembodiments mentioned herein, the temperature of ther-composition-containing effluent from the furnace can be reduced by 35to 485° C., 35 to 375° C., or 90 to 550° C. to a temperature of 500 to760° C. The cooling step is performed immediately after the effluentstream leaves the furnace such as, for example, within 1 to 30, 5 to 20,or 5 to 15 milliseconds. In an embodiment or in combination with any ofthe embodiments mentioned herein, the quenching step is performed in aquench zone 710 via indirect heat exchange with high-pressure water orsteam in a heat exchanger (sometimes called a transfer line exchanger asshown in FIG. 5 as TLE 340 and FIG. 8 as TLE 680), while, in otherembodiments, the quench step is carried out by directly contacting theeffluent with a quench liquid 712 (as generally shown in FIG. 9). Thetemperature of the quench liquid can be at least 65, or at least 80, orat least 90, or at least 100, in each case ° C. and/or not more than210, or not more than 180, or not more than 165, or not more than 150,or not more than 135, in each case ° C. When a quench liquid is used,the contacting may occur in a quench tower and a liquid stream may beremoved from the quench tower comprising gasoline and other similarboiling-range hydrocarbon components. In some cases, quench liquid maybe used when the cracker feed is predominantly liquid, and a heatexchanger may be used when the cracker feed is predominantly vapor.

The resulting cooled effluent stream is then vapor liquid separated andthe vapor is compressed in a compression zone 720, such as in a gascompressor having, for example, between 1 and 5 compression stages withoptional inter-stage cooling and liquid removal. The pressure of the gasstream at the outlet of the first set of compression stages is in therange of from 7 to 20 bar gauge (barg), 8.5 to 18 psig (0.6˜1.3 barg),or 9.5 to 14 barg.

The resulting compressed stream is then treated in an acid gas removalzone 722 for removal of acid gases, including CO, CO2, and H2S bycontact with an acid gas removal agent. Examples of acid gas removalagents can include, but are not limited to, caustic and various types ofamines. In an embodiment or in combination with any of the embodimentsmentioned herein, a single contactor may be used, while, in otherembodiments, a dual column absorber-stripper configuration may beemployed.

The treated compressed olefin-containing stream may then be furthercompressed in another compression zone 724 via a compressor, optionallywith inter-stage cooling and liquid separation. The resulting compressedstream, which has a pressure in the range of 20 to 50 barg, 25 to 45barg, or 30 to 40 barg. Any suitable moisture removal method can be usedincluding, for example, molecular sieves or other similar process to drythe gas in a drying zone 726. The resulting stream 730 may then bepassed to the fractionation section, wherein the olefins and othercomponents may be separated in to various high-purity product orintermediate streams.

Turning now to FIG. 10, a schematic depiction of the main steps of thefractionation section is provided. In an embodiment or in combinationwith any of the embodiments mentioned herein, the initial column of thefractionation train may not be a demethanizer 810, but may be adeethanizer 820, a depropanizer 840, or any other type of column. Asused herein, the term “demethanizer,” refers to a column whose light keyis methane. Similarly, “deethanizer,” and “depropanizer,” refer tocolumns with ethane and propane as the light key component,respectively.

As shown in FIG. 10, a feed stream 870 from the quench section mayintroduced into a demethanizer (or other) column 810, wherein themethane and lighter (CO, CO2, H2) components 812 are separated from theethane and heavier components 814. The demethanizer is operated at atemperature of at least −145, or at least −142, or at least −140, or atleast −135, in each case ° C. and/or not more than −120, −125, −130,−135° C. The bottoms stream 814 from the demethanizer column, whichincludes at least 50, or at least 55, or at least 60, or at least 65, orat least 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95 or at least 99, in each case percent of the totalamount of ethane and heavier components introduced into the column, isthen introduced into a deethanizer column 820, wherein the C2 andlighter components 816 are separated from the C3 and heavier components818 by fractional distillation. The de-ethanizer 820 can be operatedwith an overhead temperature of at least −35, or at least −30, or atleast −25, or at least −20, in each case ° C. and/or not more than −5,−10, −10, −20° C., and an overhead pressure of at least 3, or at least5, or at least 7, or at least 8, or at least 10, in each case bargand/or not more than 20, or not more than 18, or not more than 17, ornot more than 15, or not more than 14, or not more than 13, in each casebarg. The deethanizer column 820 recovers at least 60, or at least 65,or at least 70, or at least 75, or at least 80, or at least 85, or atleast 90, or at least 95, or at least 97, or at least 99, in each casepercent of the total amount of C2 and lighter components introduced intothe column in the overhead stream. In an embodiment or in combinationwith any of the embodiments mentioned herein, the overhead stream 816removed from the deethanizer column comprises at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, in eachcase weight percent of ethane and ethylene, based on the total weight ofthe overhead stream.

As shown in FIG. 10, the C2 and lighter overhead stream 816 from thedeethanizer 820 is further separated in an ethane-ethylene fractionatorcolumn (ethylene fractionator) 830. In the ethane-ethylene fractionatorcolumn 830, an ethylene and lighter component stream 822 can bewithdrawn from the overhead of the column 830 or as a side stream fromthe top ½ of the column, while the ethane and any residual heaviercomponents are removed in the bottoms stream 824. The ethylenefractionator 830 may be operated at an overhead temperature of at least−45, or at least −40, or at least −35, or at least −30, or at least −25,or at least −20, in each case ° C. and/or not more than −15, or not morethan −20, or not more than −25, in each case ° C., and an overheadpressure of at least 10, or at least 12, or at least 15, in each casebarg and/or not more than 25, 22, 20 barg. The overhead stream 822,which is enriched in ethylene, can include at least 70, or at least 75,or at least 80, or at least 85, or at least 90, or at least 95, or atleast 97, or at least 98, or at least 99, in each case weight percentethylene, based on the total weight of the stream and may be sent todownstream processing unit for further processing, storage, or sale. Theoverhead ethylene stream 822 produced during the cracking of a crackerfeedstock containing r-pyoil is a r-ethylene composition or stream. Inan embodiment or in combination with any of the embodiments mentionedherein, the r-ethylene stream may be used to make one or morepetrochemicals.

The bottoms stream from the ethane-ethylene fractionator 824 may includeat least 40, or at least 45, or at least 50, or at least 55, or at least60, or at least 65, or at least 70, or at least 75, or at least 80, orat least 85, or at least 90, or at least 95, or at least 98, in eachcase weight percent ethane, based on the total weight of the bottomsstream. All or a portion of the recovered ethane may be recycled to thecracker furnace as additional feedstock, alone or in combination withthe r-pyoil containing feed stream, as discussed previously.

The liquid bottoms stream 818 withdrawn from the deethanizer column,which may be enriched in C3 and heavier components, may be separated ina depropanizer 840, as shown in FIG. 10. In the depropanizer 840, C3 andlighter components are removed as an overhead vapor stream 826, while C4and heavier components may exit the column in the liquid bottoms 828.The depropanizer 840 can be operated with an overhead temperature of atleast 20, or at least 35, or at least 40, in each case ° C. and/or notmore than 70, 65, 60, 55° C., and an overhead pressure of at least 10,or at least 12, or at least 15, in each case barg and/or not more than20, or not more than 17, or not more than 15, in each case barg. Thedepropanizer column 840 recovers at least 60, or at least 65, or atleast 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, or at least 97, or at least 99, in each case percentof the total amount of C3 and lighter components introduced into thecolumn in the overhead stream 826. In an embodiment or in combinationwith any of the embodiments mentioned herein, the overhead stream 826removed from the depropanizer column 840 comprises at least or at least50, or at least 55, or at least 60, or at least 65, or at least 70, orat least 75, or at least 80, or at least 85, or at least 90, or at least95, or at least 98, in each case weight percent of propane andpropylene, based on the total weight of the overhead stream 826.

The overhead stream 826 from the depropanizer 840 are introduced into apropane-propylene fractionator (propylene fractionator) 860, wherein thepropylene and any lighter components are removed in the overhead stream832, while the propane and any heavier components exit the column in thebottoms stream 834. The propylene fractionator 860 may be operated at anoverhead temperature of at least 20, or at least 25, or at least 30, orat least 35, in each case ° C. and/or not more than 55, 50, 45, 40° C.,and an overhead pressure of at least 12, or at least 15, or at least 17,or at least 20, in each case barg and/or not more than 20, or not morethan 17, or not more than 15, or not more than 12, in each case barg.The overhead stream 860, which is enriched in propylene, can include atleast 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, or at least 97, or at least 98, or at least 99, ineach case weight percent propylene, based on the total weight of thestream and may be sent to downstream processing unit for furtherprocessing, storage, or sale. The overhead propylene stream producedduring the cracking of a cracker feedstock containing r-pyoil is ar-propylene composition or stream. In an embodiment or in combinationwith any of the embodiments mentioned herein, the stream may be used tomake one or more petrochemicals.

The bottoms stream 834 from the propane-propylene fractionator 860 mayinclude at least 40, or at least 45, or at least 50, or at least 55, orat least 60, or at least 65, or at least 70, or at least 75, or at least80, or at least 85, or at least 90, or at least 95, or at least 98, ineach case weight percent propane, based on the total weight of thebottoms stream 834. All or a portion of the recovered propane may berecycled to the cracker furnace as additional feedstock, alone or incombination with r-pyoil, as discussed previously.

Referring again to FIG. 10, the bottoms stream 828 from the depropanizercolumn 840 may be sent to a debutanizer column 850 for separating C4components, including butenes, butanes and butadienes, from C5+components. The debutanizer can be operated with an overhead temperatureof at least 20, or at least 25, or at least 30, or at least 35, or atleast 40, in each case ° C. and/or not more than 60, or not more than65, or not more than 60, or not more than 55, or not more than 50, ineach case ° C. and an overhead pressure of at least 2, or at least 3, orat least 4, or at least 5, in each case barg and/or not more than 8, ornot more than 6, or not more than 4, or not more than 2, in each casebarg. The debutanizer column recovers at least 60, or at least 65, or atleast 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, or at least 97, or at least 99, in each case percentof the total amount of C4 and lighter components introduced into thecolumn in the overhead stream 836. In an embodiment or in combinationwith any of the embodiments mentioned herein, the overhead stream 836removed from the debutanizer column comprises at least 30, or at least35, or at least 40, or at least 45, or at least 50, or at least 55, orat least 60, or at least 65, or at least 70, or at least 75, or at least80, or at least 85, or at least 90, or at least 95, in each case weightpercent of butadiene, based on the total weight of the overhead stream.The overhead stream 836 produced during the cracking of a crackerfeedstock containing r-pyoil is a r-butadiene composition or stream. Thebottoms stream 838 from the debutanizer includes mainly C5 and heaviercomponents, in an amount of at least 50, or at least 60, or at least 70,or at least 80, or at least 90, or at least 95 weight percent, based onthe total weight of the stream. The debutanizer bottoms stream 838 maybe sent for further separation, processing, storage, sale or use.

The overhead stream 836 from the debutanizer, or the C4s, can besubjected to any conventional separation methods such as extraction ordistillation processes to recover a more concentrated stream ofbutadiene.

Production and Use of Oxo Glycols

In one embodiment or in combination with any of the mentionedembodiments, there is now provided a method for processing recyclecontent olefin including, for example, recycle content propylene, byfeeding the r-olefin to a reactor in which is made r-aldehydes, whichare subsequently condensed in the presence of a catalyst and optionallyhydrogenated to form oxo glycols. In some embodiments, the r-aldehydesmay include r-butyraldehyde, and in particular, isobutyraldehyde, whichmay react with formaldehyde and optionally hydrogen to form oxo glycols,including 2,2-dimethyl-1,3-propanediol.

In one embodiment or in combination with any of the mentionedembodiments, the concentration of r-olefin, introduced into a reactorvessel is at least 90 wt. %, or at least 95 wt. %, or at least 97 wt. %,or at least 99 wt. %, based on the weight of the olefin composition fedto the aldehyde reactor.

Similarly, in one embodiment or in combination with any of the mentionedembodiments, the concentration of r-aldehyde, introduced into a reactorvessel for reacting aldehyde to form an oxo glycol is at least 90 wt. %,or at least 95 wt. %, or at least 97 wt. %, or at least 99 wt. %, basedon the weight of the aldehyde composition fed to the oxo glycol reactor.

In one embodiment or in combination with any of the mentionedembodiments, the olefin or aldehyde fed to the reaction vessel does notcontain recycle content. In another embodiment, at least a portion ofthe olefin or aldehyde composition fed to the reaction vessel is deriveddirectly or indirectly from the cracking of r-pyoil or obtained fromr-pygas. For example, at least 0.005 wt. %, or at least 0.01 wt. %, orat least 0.05 wt. %, or at least 0.1 wt. %, or at least 0.15 wt. %, orat least 0.2 wt. %, or at least 0.25 wt. %, or at least 0.3 wt. %, or atleast 0.35 wt. %, or at least 0.4 wt. %, or at least 0.45 wt. %, or atleast 0.5 wt. %, or at least 0.6 wt. %, or at least 0.7 wt. %, or atleast 0.8 wt. %, or at least 0.9 wt. %, or at least 1 wt. %, or at least2 wt. %, or at least 3 wt. %, or at least 4 wt. %, or at least 5 wt. %,or at least 6 wt. %, or at least 7 wt. %, or at least 8 wt. %, or atleast 9 wt. %, or at least 10 wt. %, or at least 11 wt. %, or at least13 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt.%, or at least 30 wt. %, or at least 35 wt. %, or at least 40 wt. %, orat least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or atleast 60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least90 wt. %, or at least 95 wt. %, or at least 98 wt. %, or at least 99 wt.%, or 100 wt. % of the olefin composition is r-olefin or pr-olefin orr-aldehyde or pr-aldehyde.

In addition, or in the alternative, up to 100 wt. %, or up to 98 wt. %,or up to 95 wt. %, or up to 90 wt. %, or up to 80 wt. %, or up to 75 wt.%, or up to 70 wt. %, or up to 60 wt. %, or up to 50 wt. %, or up to 40wt. %, or up to 30 wt. %, or up to 20 wt. %, or up to 10 wt. %, or up to8 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. %, or up to2 wt. %, or up to 1 wt. %, or up to 0.8 wt. %, or up to 0.7 wt. %, or upto 0.6 wt. %, or up to 0.5 wt. %, or up to 0.4 wt. %, or up to 0.3 wt.%, or up to 0.2 wt. %, or up to 0.1 wt. %, or up to 0.09 wt. %, or up to0.07 wt. %, or up to 0.05 wt. %, or up to 0.03 wt. %, or up to 0.02 wt.%, or up to 0.01 wt. % of the olefin composition is pr-olefin, based onthe weight the olefin composition fed to the reaction vessel.

Alternatively, or in addition, at least 0.005 wt. %, or at least 0.01wt. %, or at least 0.05 wt. %, or at least 0.1 wt. %, or at least 0.15wt. %, or at least 0.2 wt. %, or at least 0.25 wt. %, or at least 0.3wt. %, or at least 0.35 wt. %, or at least 0.4 wt. %, or at least 0.45wt. %, or at least 0.5 wt. %, or at least 0.6 wt. %, or at least 0.7 wt.%, or at least 0.8 wt. %, or at least 0.9 wt. %, or at least 1 wt. %, orat least 2 wt. %, or at least 3 wt. %, or at least 4 wt. %, or at least5 wt. %, or at least 6 wt. %, or at least 7 wt. %, or at least 8 wt. %,or at least 9 wt. %, or at least 10 wt. %, or at least 11 wt. %, or atleast 13 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least25 wt. %, or at least 30 wt. %, or at least 35 wt. %, or at least 40 wt.%, or at least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, orat least 60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or atleast 90 wt. %, or at least 95 wt. %, or at least 98 wt. %, or at least99 wt. %, or 100 wt. % of the aldehyde composition is r-aldehyde orpr-aldehyde.

In addition, or in the alternative, up to 100 wt. %, or up to 98 wt. %,or up to 95 wt. %, or up to 90 wt. %, or up to 80 wt. %, or up to 75 wt.%, or up to 70 wt. %, or up to 60 wt. %, or up to 50 wt. %, or up to 40wt. %, or up to 30 wt. %, or up to 20 wt. %, or up to 10 wt. %, or up to8 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. %, or up to2 wt. %, or up to 1 wt. %, or up to 0.8 wt. %, or up to 0.7 wt. %, or upto 0.6 wt. %, or up to 0.5 wt. %, or up to 0.4 wt. %, or up to 0.3 wt.%, or up to 0.2 wt. %, or up to 0.1 wt. %, or up to 0.09 wt. %, or up to0.07 wt. %, or up to 0.05 wt. %, or up to 0.03 wt. %, or up to 0.02 wt.%, or up to 0.01 wt. % of the aldehyde composition is r-aldehyde orpr-aldehyde, based on the weight the composition fed to the reactionvessel.

In each case, the stated amounts are also applicable to not only olefinor aldehyde as fed into the reactor, but alternatively or in addition,to the pr-olefin or pr-aldehyde stock supplied to a manufacturer of theoxo glycol, or can be used as a basis for associating or calculating theamount of recycle content in pr-olefin or pr-aldehyde, such as whenblending a source of pr-olefin or pr-aldehyde with non-recycle contentolefin or aldehyde to make an olefin or aldehyde composition havingpr-olefin or pr-aldehyde in quantities mentioned above.

In one embodiment or in combination with any of the mentionedembodiments, the oxo glycol composition has associated with it, orcontains, or is labelled, advertised, or certified as containing recyclecontent in an amount of at least 0.01 wt. %, or at least 0.05 wt. %, orat least 0.1 wt. %, or at least 0.5 wt. %, or at least 0.75 wt. %, or atleast 1 wt. %, or at least 1.25 wt. %, or at least 1.5 wt. %, or atleast 1.75 wt. %, or at least 2 wt. %, or at least 2.25 wt. %, or atleast 2.5 wt. %, or at least 2.75 wt. %, or at least 3 wt. %, or atleast 3.5 wt. %, or at least 4 wt. %, or at least 4.5 wt. %, or at least5 wt. %, or at least 6 wt. %, or at least 7 wt. %, or at least 10 wt. %,or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt. %, or atleast 30 wt. %, or at least 35 wt. %, or at least 40 wt. %, or at least45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or at least 60 wt.%, or at least 65 wt. % and/or the amount can be up to 100 wt. %, or upto 95 wt. %, or up to 90 wt. %, or up to 80 wt. %, or up to 70 wt. %, orup to 60 wt. %, or up to 50 wt. %, or up to 40 wt. %, or up to 30 wt. %,or up to 25 wt. %, or up to 22 wt. %, or up to 20 wt. %, or up to 18 wt.%, or up to 16 wt. %, or up to 15 wt. %, or up to 14 wt. %, or up to 13wt. %, or up to 11 wt. %, or up to 10 wt. %, or up to 8 wt. %, or up to6 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. %, or up to2 wt. %, or up to 1 wt. %, or up to 0.9 wt. %, or up to 0.8 wt. %, or upto 0.7 wt. %, based on the weight of the oxo glycol composition.

The recycle content associated with the oxo glycol can be established byapplying a recycle content value to the oxo glycol, such as throughdeducting the recycle content value from a recycle inventory populatedwith allotments (credit or allocation) or by reacting an r-olefin orr-aldehyde feedstock to make r-oxo glycol. The allotment can becontained in a recycle inventory created, maintained or operated by orfor the oxo glycol manufacturer. The allotments are obtained from anysource along any manufacturing chain of products. In one embodiment, theorigin of the allotment is derived indirectly from pyrolyzing recycledwaste, or from cracking r-pyoil or from r-pygas.

The amount of recycle content in an r-olefin or r-aldehyde raw materialfed to an oxo glycol reactor, or the amount of recycle content appliedto the r-oxo glycol, or the amount of r-olefin or r-aldehyde needed tofeed the reactor to claim a desired amount of recycle content in the oxoglycol in the event that all the recycle content from the r-olefin orr-aldehyde is applied to the oxo glycol, can be determined or calculatedby any of the following methods:

-   -   (i) the amount of an allotment associated with the r-olefin or        r-aldehyde used to feed the reactor applied determined by the        amount certified or declared by the supplier of the olefin or        aldehyde composition transferred to the manufacturer of the oxo        glycol, or    -   (ii) the amount of allocation declared by the oxo glycol        manufacturer as fed to the oxo glycol reactor, or    -   (iii) using a mass balance approach to back-calculate the        minimum amount of recycle content in the feedstock from an        amount of recycle content declared, advertised, or accounted for        by the manufacturer, whether or not accurate, as applied to the        oxo glycol product, or    -   (iv) blending of non-recycle content with recycle content        feedstock olefin or aldehyde or associating recycle content to a        portion of the feedstock, using pro-rata mass approach.

Satisfying any one of the methods (i)-(iv) is sufficient to establishthe portion of r-olefin or r-aldehyde that is derived directly orindirectly from recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste. Inthe event that an r-olefin or r-aldehyde feed is blended with a recyclefeed from other recycle sources, a pro-rata approach to the mass ofr-olefin or r-aldehyde directly or indirectly obtained from recycledwaste, the pyrolysis of recycled waste, pyrolysis gas produced from thepyrolysis of recycled waste, and/or the cracking of r-pyoil producedfrom the pyrolysis of recycled waste to the mass of recycle olefin oraldehyde from other sources is adopted to determine the percentage inthe declaration attributable to r-olefin or r-aldehyde obtained directlyor indirectly from recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste.

Methods (i) and (ii) need no calculation since they are determined basedon what the olefin or aldehyde manufacturer or oxo glycol manufactureror suppliers declare, claim, or otherwise communicate to each other orthe public. Methods (iii) and (iv) are calculated.

In one embodiment or in combination with any of the mentionedembodiments, the minimum amount of recycle content olefin or aldehydefed to the reactor can be determined by knowing the amount of recyclecontent associated with the end product oxo glycol and assuming that theentire recycle content in the oxo glycol is attributable to the r-olefinor r-aldehyde fed to the reactor and none to any other components in thereaction zone.

The minimum portion of r-olefin or r-aldehyde content derived directlyor indirectly from recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste, tomake an oxo glycol product associated with a particular amount ofrecycle content, can be calculated as:

$P = {( \frac{\% D}{100} ) \times ( \frac{Pm}{Rm} ) \times ( \frac{100}{Y} ) \times 100}$

where P means the minimum portion of r-olefin or r-aldehyde deriveddirectly or indirectly recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste, and

% D means the percentage of recycle content declared in product r-oxoglycol, and

Pm means the molecular weight of product oxo glycol, and

Rm means the molecular weight of reactant olefin or aldehyde as a moietyin oxo glycol product, not to exceed the molecular weight of thereactant olefin or aldehyde, and

Y means the percent yield of the product, e.g. oxo glycol, determined asan average annual yield regardless of whether or not the feedstock isr-olefin or r-aldehyde. If an average annual yield is not known, theyield can be assumed to be industry average using the same processtechnology.

The amount of recycle content in the r-olefin or r-aldehyde feed can begreater than the minimum, resulting in excess recycle content left overif for a given designation of recycle content in the oxo glycol. In sucha case, the remainder of recycle content available may be reserved in arecycle inventory. The excess recycle content may be stored in a recycleinventory and applied to other oxo glycol products that either are notmade with r-olefin or r-aldehyde or with a deficient amount of r-olefinor r-aldehyde recycle content relative to the amount of recycle contentone desires to apply to the oxo glycol. However, whether or not ther-olefin or r-aldehyde feedstock actually was designated by themanufacturer of the oxo glycol as containing the minimum amount ofrecycle content, an r-oxo glycol designated as containing a certainrecycle content is nevertheless deemed to have been made from anr-olefin or r-aldehyde feedstock containing the minimum recycle contentby the calculation method described above.

In the case of a pro-rata mass approach in method (iv), the portion ofr-olefin or r-aldehyde derived directly or indirectly from recycledwaste, the pyrolysis of recycled waste, pyrolysis gas produced from thepyrolysis of recycled waste, and/or the cracking of r-pyoil producedfrom the pyrolysis of recycled waste would be calculated on the basis ofthe mass of recycle content available to the oxo glycol manufacturer byway of purchase or transfer or created in case the olefin or aldehyde isintegrated into r-olefin or r-aldehyde production, that is attributed tothe feedstock on a daily run divided by the mass of the r-olefin orr-aldehyde feedstock, or:

$P = {\frac{Mr}{Ma} \times 100}$

where P means the percentage of recycle content in the oxo glycolfeedstock stream, and

where Mr is the mass of recycle content attributed to the r-olefin orr-aldehyde stream on a daily basis, and

Ma is the mass of the entire olefin or aldehyde feedstock used to makeoxo glycol on the corresponding day.

For example, if an oxo glycol manufacturer has available 1000 kg of arecycle allocation or credit that has its origin in pyrolyzing recycledwaste, and the oxo glycol manufacturer elects to attribute 10 kg of therecycle allocation to an olefin or aldehyde feedstock used to make theoxo glycol, and the olefin or aldehyde feedstock employs 100 kg per dayto make oxo glycol, the portion P of the r-olefin or r-aldehydefeedstock derived directly or indirectly from cracking pyoil would be 10kg/100 kg, or 10 wt %. The olefin or aldehyde feedstock compositionwould be considered to be an r-olefin or r-aldehyde composition becausea portion of the recycle allocation is applied to the olefin or aldehydefeedstock used to make the oxo glycol.

In another embodiment, there is provided a variety of methods forapportioning the recycle content among the various products made by anoxo glycol manufacturer or the products made by any one entity or acombinations of entities among the Family of Entities of which the oxoglycol manufacturer is a part. For example, the oxo glycol manufacturer,of any combination or the entirety of its Family of Entities, or a Site,can:

-   -   a. adopt a symmetric distribution of recycle content values        among its product(s) based on the same fractional percentage of        recycle content in one or more feedstocks or based on the amount        of allotment received. For example, if 5 wt. % of the olefin or        aldehyde feedstock is r-olefin or r-aldehyde, or if the        allotment value is 5 wt. % of the entire olefin or aldehyde        feedstock, then all oxo glycol made with the olefin or aldehyde        feedstock may contain 5 wt. % recycle content value. In this        case, the amount of recycle content in the products is        proportional to the amount of recycle content in the feedstock        to make the products; or    -   b. adopt an asymmetric distribution of recycle content values        among its product(s) based on the same fractional percentage of        recycle content in the one or more feedstocks or based on the        amount of allotment received. For example, if 5 wt. % of the        olefin or aldehyde feedstock is r-olefin or r-aldehyde, or if        the allotment value is 5 wt. % of the entire olefin or aldehyde        feedstock, then one volume or batch of oxo glycol can receive a        greater amount of recycle content value that other batches or        volume of oxo glycol made, provided that the total amount of        recycle content does not exceed the total amount of r-olefin or        r-aldehyde or allotment received, or the total amount of recycle        content in the recycle inventory. One batch of oxo glycol can        contain 5% recycle content by mass, and another batch can        contain zero 0% recycle content, even though both volumes are        made from the same volume of olefin or aldehyde feedstock. In        the asymmetric distribution of recycle content, a manufacturer        can tailor the recycle content to volumes of oxo glycol sold as        needed among customers, thereby providing flexibility among        customers some of whom may need more recycle content than others        in an oxo glycol volume.

Both the symmetric distribution and the asymmetric distribution ofrecycle content can be proportional on a site wide basis, or on amulti-site basis. In one embodiment or in combination with any of thementioned embodiments, the recycle content input (recycle contentfeedstock or allotments) can be to a Site, and recycle content valuesfrom said inputs are applied to one or more products made at the sameSite, and at least one of the products made at the Site is oxo glycol,and optionally at least a portion of the recycle content value isapplied to the oxo glycol products. The recycle content values can beapplied symmetrically or asymmetrically to the products at the Site. Therecycle content values can be applied across different oxo glycolvolumes symmetrically or asymmetrically, or applied across a combinationof oxo glycol and other products made at the Site. For example, arecycle content value is transferred to a recycle inventory at a Site,created at a Site, or a feedstock containing recycle content value isreacted at a Site (collectively the “a recycle input”), and recyclecontent values obtained from said inputs are:

-   -   a. distributed symmetrically across at least a portion or across        all oxo glycol volume made at the Site over a period of time        (e.g. within 1 week, or within 1 month, or within 6 months, or        within the same calendar year, or continuously); or    -   b. distributed symmetrically across at least a portion or across        all oxo glycol volume made at the Site and across at least a        portion or across a second different product made at the same        Site, each over the same period of time (e.g. within 1 week, or        within 1 month, or within 6 months, or within the same calendar        year, or continuously); or    -   c. recycle content is distributed symmetrically across all        products to which recycle content is actually applied that are        made at the Site, over the same period of time (e.g. within the        same day, or within 1 week, or within 1 month, or within 6        months, or within the same calendar year, or continuously).        While a variety of products can be made at a Site, in this        option, not all product have to receive a recycle content value,        but for all products that do receive or to which are applied a        recycle content value, the distribution is symmetrical; or    -   d. distributed asymmetrically across at least two oxo glycol        volumes made at the same Site, optionally either over the same        period of time (e.g. within 1 day, or within 1 week, or within 1        month, or within 6 months, or within a calendar year, or        continuously), or as sold to at least two different customers.        For example, one volume of oxo glycol made can have a greater        recycle content value than a second volume of oxo glycol made at        the Site, or one volume of oxo glycol made at the Site and sold        to one customer can have a greater recycle content value than a        second volume of oxo glycol made at the Site and sold to a        second different customer, or    -   e. distributed asymmetrically across at least one volume of oxo        glycol and at least one volume of a different product, each made        at the same Site, optionally either over the same period of time        (e.g. within 1 day, or within 1 week, or within 1 month, or        within 6 months, or within a calendar year, or continuously), or        as sold to at least two different customers.

In one embodiment or in combination with any of the mentionedembodiments, the recycle content input or creation (recycle contentfeedstock or allotments) can be to or at a first Site, and recyclecontent values from said inputs are transferred to a second Site andapplied to one or more products made at a second Site, and at least oneof the products made at the second Site is oxo glycol, and optionally atleast a portion of the recycle content value is applied to oxo glycolproducts made at the second Site. The recycle content values can beapplied symmetrically or asymmetrically to the products at the secondSite. The recycle content values can be applied across different oxoglycol volumes symmetrically or asymmetrically, or applied across acombination of oxo glycol and other products made at the second Site.For example, a recycle content value is transferred to a recycleinventory at a first Site, created at a first Site, or a feedstockcontaining recycle content value is reacted at a first Site(collectively the “a recycle input”), and recycle content valuesobtained from said inputs are:

-   -   a. distributed symmetrically across at least a portion or across        all oxo glycol volume made at a second Site over a period of        time (e.g. within 1 week, or within 1 month, or within 6 months,        or within the same calendar year, or continuously); or    -   b. distributed symmetrically across at least a portion or across        all oxo glycol volume made at the second Site and across at        least a portion or across a second different product made at the        same second Site, each over the same period of time (e.g. within        1 week, or within 1 month, or within 6 months, or within the        same calendar year, or continuously); or    -   c. recycle content is distributed symmetrically across all        products to which recycle content is actually applied that are        made at the second Site, over the same period of time (e.g.        within the same day, or within 1 week, or within 1 month, or        within 6 months, or within the same calendar year, or        continuously). While a variety of products can be made at a        second Site, in this option, not all products have to receive a        recycle content value, but for all products that do receive or        to which are applied a recycle content value, the distribution        is symmetrical; or    -   d. distributed asymmetrically across at least two oxo glycol        volumes made at the same second Site, optionally either over the        same period of time (e.g. within 1 day, or within 1 week, or        within 1 month, or within 6 months, or within a calendar year,        or continuously), or as sold to at least two different        customers. For example, one volume of oxo glycol made can have a        greater recycle content value than a second volume of oxo glycol        each made at the second Site, or one volume of oxo glycol made        at the second Site and sold to one customer can have a greater        recycle content value than a second volume of oxo glycol made at        the second Site and sold to a second different customer, or    -   e. distributed asymmetrically across at least one volume of oxo        glycol and at least one volume of a different product, each made        at the same second Site, optionally either over the same period        of time (e.g. within 1 day, or within 1 week, or within 1 month,        or within 6 months, or within a calendar year, or continuously),        or as sold to at least two different customers.

In one embodiment or in combination with any of the mentionedembodiments, the oxo glycol manufacturer, or one among its Family ofEntities, can make oxo glycol, or process an olefin or aldehyde, orprocess olefin or aldehyde and make an r-oxo glycol, or make r-oxoglycol, by obtaining any source of an olefin or aldehyde compositionfrom a supplier, whether or not such olefin or aldehyde composition hasany direct or indirect recycle content, and either:

-   -   i. from the same supplier of the olefin or aldehyde composition,        also obtain a recycle content allotment, or    -   ii. from any person or entity, obtaining a recycle content        allotment without a supply of an olefin or aldehyde composition        from the person or entity transferring the recycle content        allotment.

The allotment in (i) is obtained from an olefin or aldehyde supplier,and the olefin or aldehyde supplier also supplies olefin or aldehyde tothe oxo glycol manufacturer or within its Family of Entities. Thecircumstance described in (i) allows an oxo glycol manufacturer toobtain a supply of an olefin or aldehyde composition that is anon-recycle content olefin or aldehyde, yet obtain a recycle contentallotment from the olefin or aldehyde supplier. In one embodiment or incombination with any of the mentioned embodiments, the olefin oraldehyde supplier transfers a recycle content allotment to the oxoglycol manufacturer and a supply of olefin or aldehyde to the oxo glycolmanufacturer, where the recycle content allotment is not associated withthe olefin or aldehyde supplied, or even not associated with any olefinor aldehyde made by the olefin or aldehyde supplier. The recycle contentallotment does not have to be tied to an amount of recycle content in anolefin or aldehyde composition or to any compound used to make oxoglycol, but rather the recycle content allotment transferred by theolefin or aldehyde supplier can be associated with other productsderived directly or indirectly from recycled waste, the pyrolysis ofrecycled waste, pyrolysis gas produced from the pyrolysis of recycledwaste, and/or the cracking of r-pyoil produced from the pyrolysis ofrecycled waste or the recycle content of any downstream compoundsobtained from the pyrolysis of recycled waste, such as r-ethylene,r-propylene, r-butadiene, r-aldehydes, r-alcohols, r-benzene, etc. Forexample, the olefin or aldehyde supplier can transfer to the oxo glycolmanufacturer a recycle content associated with r-olefin or r-aldehydeand also supply a quantity of olefin or aldehyde even though r-olefin orr-aldehyde was not used in the synthesis of the olefin or aldehyde. Thisallows flexibility among the olefin or aldehyde supplier and oxo glycolmanufacturer to apportion a recycle content among the variety ofproducts they each make.

In one embodiment or in combination with any of the mentionedembodiments, the olefin or aldehyde supplier transfers a recycle contentallotment to the oxo glycol manufacturer and a supply of olefin oraldehyde to the oxo glycol manufacturer, where the recycle contentallotment is associated with the olefin or aldehyde. In this case, theolefin or aldehyde transferred does not have to be an r-olefin orr-aldehyde (one that is derived directly or indirectly from thepyrolysis of recycled waste); rather the olefin or aldehyde supplied bythe supplier can be any olefin or aldehyde such as a non-recycle contentolefin or aldehyde, so long as the allocation supplied is associatedwith a manufacture of olefin or aldehyde. Optionally, the olefin oraldehyde being supplied can r-olefin or r-aldehyde and at least aportion of the recycle content allotment being transferred can be therecycle content in the r-olefin or r-aldehyde. The recycle contentallotment transferred to the oxo glycol manufacturer can be up frontwith the olefin or aldehyde supplied in installments, or with eacholefin or aldehyde installment, or apportioned as desired among theparties.

The allotment in (ii) is obtained by the oxo glycol manufacturer (or itsFamily of Entities) from any person or entity without obtaining a supplyof olefin or aldehyde from the person or entity. The person or entitycan be an olefin or aldehyde manufacturer that does not supply olefin oraldehyde to the oxo glycol manufacturer or its Family of Entities, orthe person or entity can be a manufacturer that does not make olefin oraldehyde.

In either case, the circumstances of (ii) allows an oxo glycolmanufacturer to obtain a recycle content allotment without having topurchase any olefin or aldehyde from the entity supplying the recyclecontent allotment. For example, the person or entity may transfer arecycle content allotment through a buy/sell model or contract to theoxo glycol manufacturer or its Family of Entities without requiringpurchase or sale of a allotment (e.g. as a product swap of products thatare not olefin or aldehyde), or the person or entity may outright sellthe allotment to the oxo glycol manufacturer or one among its Family ofEntities. Alternatively, the person or entity may transfer a product,other than olefin or aldehyde, along with its associated recycle contentallotment to the oxo glycol manufacturer. This can be attractive to anoxo glycol manufacturer that has a diversified business making a varietyof products other than oxo glycol requiring raw materials other thanolefin or aldehyde that the person or entity can supply to the oxoglycol manufacturer.

The oxo glycol manufacturer can deposit the allotment into a recycleinventory. The oxo glycol manufacturer also makes oxo glycol, whether ornot a recycle content is applied to the oxo glycol so made and whetheror not a recycle content value, if applied to the oxo glycol, is drawnfrom the recycle inventory. For example, the oxo glycol manufacturer, orany entity among its Family of Entities may:

-   -   a. deposit the allotment into a recycle inventory and merely        store it; or    -   b. deposit the allotment into a recycle inventory and apply a        recycle content value from the recycle inventory to products        other than oxo glycol made by the oxo glycol manufacturer, or    -   c. sell or transfer an allotment from the recycle inventory into        which the allotment obtained as noted above was deposited.

If desired, however, from that recycle inventory, any allotment can bededucted and applied to the oxo glycol product in any amount and at anytime up to the point of sale or transfer of the oxo glycol to a thirdparty. Thus, the recycle content allotment applied to the oxo glycol canbe derived directly or indirectly from pyrolyzing recycled waste, or therecycle content allotment applied to the oxo glycol is not deriveddirectly or indirectly from the pyrolysis of recycled waste.

For example, a recycle inventory of allotments can be generated having avariety of sources for creating the allotments. Some recycle contentallotments (credits) can have their origin in methanolysis of recycledwaste, or from gasification of recycled waste, or from mechanicalrecycling of waste plastic or metal recycling, and/or from pyrolyzingrecycled waste, or from any other chemical or mechanical recyclingtechnology. The recycle inventory may or may not track the origin orbasis of obtaining a recycle content, or the recycle inventory may notallow one to associate the origin or basis of an allocation to theallocation applied to oxo glycol. Thus, in this embodiment, it issufficient that a recycle content value is deducted from recycleinventory and applied to oxo glycol regardless of the source or originof the recycle content value, provided that an allotment derived frompyrolyzing recycled waste is also obtained by the oxo glycolmanufacturer as specified in step (i) or step (ii), whether or not thatallotment is actually deposited into the recycle inventory. In oneembodiment or in combination with any of the mentioned embodiments, theallotment obtained in step (i) or (ii) is deposited into a recycleinventory of allotments. In one embodiment or in combination with any ofthe mentioned embodiments, the recycle content value deducted from therecycle inventory and applied to the oxo glycol originates frompyrolyzing recycled waste.

As used throughout, the recycle inventory of allotments can be owned bythe oxo glycol manufacturer, operated by the oxo glycol manufacturer,owned or operated by other than the oxo glycol manufacturer but at leastin part for the oxo glycol manufacturer, or licensed by the oxo glycolmanufacturer. Also, as used throughout, the oxo glycol manufacturer mayalso include its Family of Entities. For example, while the oxo glycolmanufacturer may not own or operate the recycle inventory, one among itsFamily of Entities may own such a platform, or license it from anindependent vendor, or operate it for the oxo glycol manufacturer.Alternatively, an independent entity may own and/or operate the recycleinventory and for a service fee operate and/or manage at least a portionof the recycle inventory for the oxo glycol manufacturer.

In one embodiment or in combination with any of the mentionedembodiments, the oxo glycol manufacturer obtains a supply of olefin oraldehyde from a supplier, and also obtains an allotment from either (i)the supplier or (ii) from any other person or entity, where suchallotment is derived from recycled waste, the pyrolysis of recycledwaste, pyrolysis gas produced from the pyrolysis of recycled waste,and/or the cracking of r-pyoil produced from the pyrolysis of recycledwaste, and optionally the allotment is obtained from the olefin oraldehyde supplier and can even be an allotment by virtue of obtaining anr-olefin or r-aldehyde from the supplier. The oxo glycol manufacturer isdeemed to obtain the supply of olefin or aldehyde from a supplier if thesupply is obtained by a person or entity within the Family of Entitiesof the oxo glycol manufacturer. The oxo glycol manufacturer then carriesout one or more of the following steps:

-   -   a. applying the allotment to oxo glycol made by the supply of        olefin or aldehyde;    -   b. applying the allotment to oxo glycol not made by the supply        of olefin or aldehyde, such as would be the case where oxo        glycol is already made and stored in recycle inventory, or to        future made oxo glycol; or    -   c. depositing the allotment into a recycle inventory from which        is deducted a recycle content value and applying at least a        portion of the recycle content value to:        -   i. oxo glycol to thereby obtain r-oxo glycol, or        -   ii. to a compound or composition other than oxo glycol, or        -   iii. both;

whether or not r-olefin or r-aldehyde is used to make the oxo glycolcomposition, and whether or not the recycle content value applied to oxoglycol was obtained from a recycle content value in the allotmentobtained in step (i) or step (ii) or deposited into the recycleinventory; or

-   -   d. as described above, can merely be deposited into a recycle        inventory and stored.

It is not necessary in all embodiments that r-olefin or r-aldehyde isused to make the r-oxo glycol composition or that the r-oxo glycol wasobtained from a recycle content allotment associated with an olefin oraldehyde composition. Further, it is not necessary that an allotment beapplied to the feedstock for making the oxo glycol to which recyclecontent is applied. Rather, as noted above, the allotment, even ifassociated with an olefin or aldehyde composition when the olefin oraldehyde composition is obtained from a supplier, can be deposited intoan electronic recycle inventory. In one embodiment or in combinationwith any of the mentioned embodiments, however, r-olefin or r-aldehydeis used to make the r-oxo glycol composition. In one embodiment or incombination with any of the mentioned embodiments, the r-oxo glycol isobtained from a recycle content allotment associated with an alkylenecomposition. In one embodiment or in combination with any of thementioned embodiments, at least a portion of r-olefin or r-aldehydeallotments are applied to oxo glycol to make an r-oxo glycol.

The oxo glycol composition can be made from any source of an olefin oraldehyde composition, whether or not the olefin or aldehyde compositionis an r-olefin or r-aldehyde, and whether or not the olefin or aldehydeis obtained from a supplier or made by the oxo glycol manufacturer orwithin its Family of Entities. Once an oxo glycol composition is made,it can be designated as having recycle content based on and derived fromat least a portion of the allotment, again whether or not the r-olefinor r-aldehyde is used to make the r-oxo glycol composition andregardless of the source of olefin or aldehyde used to make the oxoglycol. The allocation can be withdrawn or deducted from recycleinventory. The amount of the deduction and/or applied to the oxo glycolcan correspond to any of the methods described above, e.g. a massbalance approach.

In one embodiment or in combination with any of the mentionedembodiments, a recycle content oxo glycol composition can be made byreacting an olefin or aldehyde composition obtained from any source in asynthetic process to make an oxo glycol, and a recycle content value canbe applied to at least a portion of the oxo glycol to thereby obtainr-oxo glycol. Optionally, a recycle content value can be obtained bydeducting from a recycle inventory. The entire amount of recycle contentvalue in the oxo glycol can correspond to the recycle content valuededucted from the recycle inventory. Recycle content value deducted fromthe recycle inventory can be applied to both oxo glycol and products orcompositions other than oxo glycol made by the oxo glycol manufactureror a person or entity among its Family of Entities.

The olefin or aldehyde composition can be obtained from a third party,or made by the oxo glycol manufacturer, or made by a person or entityamount the Family of Entities of the oxo glycol manufacturer andtransferred to the oxo glycol manufacturer. In another example, the oxoglycol manufacturer or its Family of Entities can have a first facilityfor making olefin or aldehyde within a first Site, and a second facilitywithin the first Site or a second facility within a second Site wherethe second facility makes oxo glycol, and transfer the olefin oraldehyde from the first facility or first Site to the second facility orsecond Site. The facilities or Sites can be in direct or indirect,continuous or discontinuous, fluid communication or pipe communicationwith each other. A recycle content value is then applied to (e.g.assigned to, designate to correspond to, attributed to, or associatedwith) the oxo glycol to make an r-oxo glycol. At least a portion of therecycle content value applied to the oxo glycol is obtained from arecycle inventory.

Optionally, one may communicate to a third party that the r-oxo glycolhas recycle content or is obtained or derived from recycled waste. Inone embodiment or in combination with any of the mentioned embodiments,one may communicate recycle content information about the oxo glycol toa third party where such recycle content information is based on orderived from at least a portion of the allocation or credit. The thirdparty may be a customer of the oxo glycol manufacturer or supplier, ormay be any other person or entity or governmental organization otherthan the entity owning the oxo glycol. The communication may electronic,by document, by advertisement, or any other means of communication.

In one embodiment or in combination with any of the mentionedembodiments, a recycle content oxo glycol composition is obtained byeither making a first r-oxo glycol or by merely possessing (e.g. by wayof purchase, transfer, or otherwise) a first r-oxo glycol already havinga recycle content, and transferring a recycle content value between arecycle inventory and the first r-oxo glycol to obtain a second r-oxoglycol having different recycle content value than the first r-oxoglycol.

In one embodiment or in combination with any of the mentionedembodiments, the transferred recycle content value described above isdeducted from the recycle inventory and applied to the first r-oxoglycol to obtain a second r-oxo glycol having a second recycle contentvalue higher than the first r-oxo glycol contains, to thereby increasethe recycle content in first r-oxo glycol.

The recycle content in the first r-oxo glycol need not be obtained froma recycle inventory, but rather can be attributed to oxo glycol by anyof the methods described herein (e.g. by virtue of using an r-olefin orr-aldehyde as a reactant feed), and the oxo glycol manufacturer may seekto further increase the recycle content in the first r-oxo glycol somade. In another example, an oxo glycol distributor may have r-oxoglycol in its inventory and seek to increase the recycle content valueof the first r-oxo glycol in its possession. The recycle content in thefirst r-oxo glycol can be increased by applying a recycle content valuewithdrawn from a recycle inventory.

The recycle content value quantity that is deducted from recycleinventory is flexible and will depend on the amount of recycle contentapplied to the oxo glycol. In one embodiment or in combination with anyof the mentioned embodiments, it is at least sufficient to correspondwith at least a portion of the recycle content in the r-oxo glycol. Thisis useful if, as noted above, a portion of the oxo glycol was made withr-olefin or r-aldehyde where the recycle content value in the r-olefinor r-aldehyde was not deposited into a recycle inventory, resulting inan r-oxo glycol and one desires to increase the recycle content in ther-oxo glycol by applying a recycle content value withdrawn from arecycle inventory; or where one possesses r-oxo glycol (by way ofpurchase, transfer, or otherwise) and desires to increase its recyclecontent value. Alternatively, the entire recycle content in the r-oxoglycol can be obtained by applying a recycle content value to the oxoglycol obtained from a recycle inventory.

The method for calculating the recycle content value is not limited, andcan include the mass balance approach or the methods of calculationdescribed above. The recycle inventory can be established on any basisand be a mix of bases. Examples of the origin for obtaining allotmentsdeposited into a recycle inventory can be from pyrolyzing recycledwaste, gasification of recycled waste, depolymerization of recycledwaste such as through hydrolysis or methanolysis, and so on. In oneembodiment or in combination with any of the mentioned embodiments, atleast a portion of the allocations deposited into the recycle inventoryis attributable to pyrolyzing recycled waste (e.g. obtained fromcracking r-pyoil or obtained from r-pygas). The recycle inventory may ormay not track the origin of recycle content value deposited into therecycle inventory. In one embodiment or in combination with any of thementioned embodiments, the recycle inventory distinguishes between arecycle content value obtained from pyrolyzing recycled waste (i.e.,pyrolysis recycle content value) and recycle content values having theirorigin in other technologies (i.e., recycle content value). This may beaccomplished simply by assigning distinguishing units of measure to therecycle content values having is origin in pyrolyzing recycled waste, ortracking the origin of the allocation by assigning or placing theallocation into a unique module, unique spreadsheet, unique column orrow, unique database, unique taggants associated with a unit of measure,and the like to as to distinguish the:

-   -   a. Origin of technology used to create the allotment, or    -   b. The type of compound having recycle content from which the        allocation is obtained, or    -   c. The supplier or Site identity, or    -   d. A combination thereof.

The recycle content value applied to the oxo glycol from the recycleinventory does not have to be obtained from allotments having theirorigin in pyrolyzing recycled waste. The recycle content values deductedfrom the recycle inventory and/or applied to the oxo glycol can bederived from any technology used to generate allocations from recycledwaste, such as through methanolysis or gasification of recycled waste.In one embodiment or in combination with any of the mentionedembodiments, however, the recycle content value applied to the oxoglycol or withdrawn/deducted from the recycle inventory have theirorigins or are derived from allotments obtained from pyrolyzing recycledwaste.

The following are examples of applying (designating, assigning, ordeclaring a recycle content) a recycle content value or allotment to oxoglycol or to an olefin or aldehyde composition:

-   -   1. Applying at least a portion of a recycle content value to an        oxo glycol composition where the recycle content value is        derived directly or indirectly with a recycle content olefin or        aldehyde, where such recycle content olefin or aldehyde is        obtained directly or indirectly from cracking r-pyoil or        obtained from r-pygas, and the olefin or aldehyde composition        used to make the oxo glycol did not contain any recycle content        or it did contain recycle content; or    -   2. Applying at least a portion of a recycle content value to an        oxo glycol composition where the recycle content value is        derived directly or indirectly from cracking r-pyoil or obtained        from r-pygas; or    -   3. Applying at least a portion of a recycle content value to an        oxo glycol composition where the recycle content value is        derived directly or indirectly with an r-olefin or r-aldehyde,        whether or not such olefin or aldehyde volume is used to make        the oxo glycol; or    -   4. Applying at least a portion of a recycle content value to an        oxo glycol composition where the recycle content value is        derived directly or indirectly with an r-olefin or r-aldehyde,        and the r-olefin or r-aldehyde is used as a feedstock to make        the r-oxo glycol to which the recycle content value is applied,        and:        -   a. all of the recycle content in the r-olefin or r-aldehyde            is applied to determine the amount of recycle content in the            oxo glycol, or        -   b. only a portion of the recycle content in the r-olefin or            r-aldehyde is applied to determine the amount of recycle            content applied to the oxo glycol, the remainder stored in            recycle inventory for use to future oxo glycol, or for            application to other existing oxo glycol made from r-olefin            or r-aldehyde not containing any recycle content, or to            increase the recycle content on an existing r-oxo glycol, or            a combination thereof, or        -   c. none of the recycle content in the r-olefin or r-aldehyde            is applied to the oxo glycol and instead is stored in a            recycle inventory, and a recycle content from any source or            origin is deducted from the recycle inventory and applied to            oxo glycol; or    -   5. Applying at least a portion of a recycle content value to an        olefin or aldehyde composition used to make an oxo glycol to        thereby obtain an r-oxo glycol, where the recycle content value        was obtained with the transfer or purchase of the same olefin or        aldehyde composition used to make the oxo glycol and the recycle        content value is associated with the recycle content in an        olefin or aldehyde composition; or    -   6. Applying at least a portion of a recycle content value to an        olefin or aldehyde composition used to make an oxo glycol to        thereby obtain an r-oxo glycol, where the recycle content value        was obtained with the transfer or purchase of the same olefin or        aldehyde composition used to make the oxo glycol and the recycle        content value is not associated with the recycle content in an        olefin or aldehyde composition but rather on the recycle content        of a compound used to make the olefin or aldehyde composition;        or    -   7. Applying at least a portion of a recycle content value to an        olefin or aldehyde composition used to make an oxo glycol to        thereby obtain an r-oxo glycol, where the recycle content value        was not obtained with the transfer or purchase of the olefin or        aldehyde composition and the recycle content value is associated        with the recycle content in the olefin or aldehyde composition;        or    -   8. Applying at least a portion of a recycle content value to an        olefin or aldehyde composition used to make an oxo glycol to        thereby obtain an r-oxo glycol, where the recycle content value        was not obtained with the transfer or purchase of the olefin or        aldehyde composition and the recycle content value is not        associated with the recycle content in the olefin or aldehyde        composition but rather with the recycle content of any compounds        used to make the olefin or aldehyde composition; or    -   9. Obtaining a recycle content value derived directly or        indirectly from pyrolyzing recycled waste, such as from cracking        of r-pyoil, or obtained from an r-pygas, or associated with an        r-composition, or associated with an r-olefin or r-aldehyde,        and:        -   a. no portion of the recycle content value is applied to an            olefin or aldehyde composition to make oxo glycol and at            least a portion is applied to oxo glycol to make an r-oxo            glycol; or        -   b. less than the entire portion is applied to an olefin or            aldehyde composition used to make oxo glycol and the            remainder is stored in recycle inventory or is applied to            future made oxo glycol or is applied to existing oxo glycol            in recycle inventory.

As used throughout, the step of deducting an allocation from a recycleinventory does not require its application to an oxo glycol product. Thededuction also does not mean that the quantity of the deductiondisappears or is removed from the inventory logs. A deduction can be anadjustment of an entry, a withdrawal, an addition of an entry as adebit, or any other algorithm that adjusts inputs and outputs based onan amount of recycle content associated with a product and one or acumulative amount of allocations on deposit in the recycle inventory.For example, a deduction can be a simple step of a reducing/debit entryfrom one column and an addition/credit to another column within the sameprogram or books, or an algorithm that automates the deductions andentries/additions and/or applications or designations to a productslate. The step of applying a recycle content value to an oxo glycolproduct also does not require the recycle content value or allocation tobe applied physically to an oxo glycol product or to any document issuedin association with the oxo glycol product sold. For example, an oxoglycol manufacturer may ship oxo glycol product to a customer andsatisfy the “application” of the recycle content value to the oxo glycolproduct by electronically transferring a recycle content credit orcertification document to the customer, or by applying a recycle contentvalue to a package or container containing the oxo glycol or r-olefin orr-aldehyde.

Some oxo glycol manufacturers may be integrated into making downstreamproducts using oxo glycol as a raw material. The integrated oxo glycolmanufacturers, and other non-integrated oxo glycol manufacturers, canalso offer to sell or sell oxo glycol on the market as containing orobtained with an amount of recycle content. The recycle contentdesignation can also be found on or in association with the downstreamproduct made with the oxo glycol.

In one embodiment or in combination with any of the mentionedembodiments, the amount of recycle content in the r-olefin or r-aldehydeor in the r-oxo glycol will be based on the allocation or creditobtained by the manufacturer of the oxo glycol composition or the amountavailable in the oxo glycol manufacturer's recycle inventory. A portionor all of the recycle content value in an allocation or credit obtainedby or in the possession of a manufacturer of oxo glycol can bedesignated and assigned to an r-olefin or r-aldehyde or r-oxo glycol ona mass balance basis. The assigned value of the recycle content to ther-olefin or r-aldehyde or r-oxo glycol should not exceed the totalamount of all allocations and/or credits available to the manufacturerof the oxo glycol or other entity authorized to assign a recycle contentvalue to the oxo glycol.

There is now also provided a method of introducing or establishing arecycle content in an oxo glycol without necessarily using an r-olefinor r-aldehyde feedstock. In this method,

-   -   a. an olefin supplier either:        -   i. cracks a cracker feedstock comprising recycle pyoil to            make an olefin or aldehyde composition at least a portion of            which is obtained by cracking said recycle pyoil (r-pyoil),            or        -   ii. makes a pygas at least a portion of which is obtained by            pyrolyzing a recycled waste stream (r-pygas), or        -   iii. both; and    -   b. an aldehyde manufacturer:        -   i. obtaining an allotment derived directly or indirectly            with said r-pyoil or said r-pygas from the supplier or a            third-party transferring said allotment,        -   ii. making an aldehyde from an olefin, and        -   iii. associating at least a portion of the allotment with at            least a portion of the aldehyde, whether or not the olefin            used to make the oxo glycol contains r-olefin; and    -   c. an oxo glycol manufacturer:        -   i. obtaining an allotment derived directly or indirectly            with said r-pyoil or said r-pygas from the supplier or a            third-party transferring said allotment,        -   ii. making an oxo glycol from an aldehyde, and        -   iii. associating at least a portion of the allotment with at            least a portion of the oxo glycol, whether or not the            aldehyde used to make the oxo glycol contains r-aldehyde.

In this method, the oxo glycol manufacturer need not purchase r-olefinor r-aldehyde from any entity or from the supplier of olefin oraldehyde, and does not require the oxo glycol manufacturer to purchaseolefin or aldehyde, r-olefin or r-aldehyde, or olefin or aldehyde from aparticular source or supplier, and does not require the oxo glycolmanufacturer to use or purchase an olefin or aldehyde composition havingr-olefin or r-aldehyde in order to successfully establish a recyclecontent in the oxo glycol composition. The olefin or aldehydemanufacturer may use any source of olefin or aldehyde and apply at leasta portion of the allocation or credit to at least a portion of theolefin or aldehyde feedstock or to at least a portion of the oxo glycolproduct. When the allocation or credit is applied to the feedstockolefin or aldehyde, this would be an example of an r-olefin orr-aldehyde feedstock indirectly derived from the cracking of r-pyoil orobtained from r-pygas. The association by the oxo glycol manufacturermay come in any form, whether by on in its recycle inventory, internalaccounting methods, or declarations or claims made to a third party orthe public.

In another embodiment, an exchanged recycle content value is deductedfrom a first r-oxo glycol and added to the recycle inventory to obtain asecond r-oxo glycol having a second recycle content value lower than thefirst r-oxo glycol contains, to thereby decrease the recycle content infirst r-oxo glycol. This embodiment, the above description concerningadding a recycle content value from a recycle inventory to a first r-oxoglycol applies in reverse to deducting a recycle content from firstr-oxo glycol and adding it to a recycle inventory.

The allotment can be obtained from a variety of sources in themanufacturing chain starting from pyrolyzing recycled waste up to makingand selling an r-olefin or r-aldehyde. The recycle content value appliedto oxo glycol or the allocation deposited into the recycle inventoryneed not be associated with r-olefin or r-aldehyde. In one embodiment orin combination with any of the mentioned embodiments, the process formaking r-oxo glycol can be flexible and allow for obtaining anallocation anywhere along the manufacturing chain to make oxo glycolstarting from pyrolyzing recycled waste. For example, one can make r-oxoglycol by:

-   -   a. pyrolyzing a pyrolysis feed comprising a recycled waste        material to thereby form a pyrolysis effluent that contains        r-pyoil and/or r-pygas. An allotment associated with the r-pyoil        or r-pygas is automatically created by creation of pyoil or        pygas from a recycled waste stream. The allotment may travel        with the pyoil or pygas, or be dissociated from the pyoil or        pygas such as by way of depositing the allotment into a recycle        inventory; and    -   b. optionally cracking a cracker feed that contains at least a        portion of the r-pyoil made in step a) to thereby produce a        cracker effluent containing r-olefin, including r-propylene; or        optionally cracking a cracker feed without r-pyoil to make        olefin, including propylene, and applying a recycle content        value to the olefin so made by deducting a recycle content value        from a recycle inventory (in the case that can be owned,        operated, or for the benefit of an olefin producer or its Family        of Entities) and applying the recycle content value to the        olefin to make r-olefin;    -   c. reacting any olefin volume in a synthetic process to make an        aldehyde composition; optionally using the olefin made in        step b) and optionally using an r-olefin made in step b) and        optionally applying a recycle content value associated the        manufacture of the aldehyde made to make r-aldehyde;    -   d. reacting any aldehyde volume in a synthetic process to make        an oxo glycol composition; optionally using the aldehyde made in        step c) and optionally using an r r-aldehyde made in step c) and        optionally applying a recycle content value associated the        manufacture of the oxo glycol made to make r-oxo glycol; and    -   e. applying a recycle content value to at least a portion of        said oxo glycol composition based on:        -   i. feeding r-olefin or r-aldehyde as a feedstock or        -   ii. depositing at least a portion of an allotment obtained            from any one or more of steps a), b), or c) into a recycle            inventory and deducting from said inventory a recycle            content value and applying at least a portion of either or            both of said values to oxo glycol to thereby obtain r-oxo            glycol.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a comprehensive process for makingrecycle content oxo glycols by:

-   -   a. making an r-olefin by either cracking the r-pyoil or        separating olefin or aldehyde from the r-pygas; and    -   b. converting at least a portion of any or said olefin to an        aldehyde; and    -   c. converting at least a portion of any or said aldehyde to an        oxo glycol; and    -   d. applying a recycle content value to said oxo glycol to make        an r-oxo glycol; and    -   e. optionally, also making an r-pyoil or r-pygas or both by        pyrolyzing a recycle feedstock

In this embodiment, all steps a)-d) can be practiced by and within aFamily of Entities, or optionally on the same Site.

In another method, the direct method, a recycle content can beintroduced or established in oxo glycol by:

-   -   a. obtaining recycle olefin composition at least a portion of        which is indirectly derived from cracking r-pyoil or indirectly        obtained from r-pygas (“r-olefin”),    -   b. making an aldehyde composition from a feedstock comprising        r-olefin,    -   c. making an oxo glycol composition from a feedstock comprising        r-aldehyde,    -   d. applying a recycle content value to at least a portion of any        oxo glycol composition made by the same entity that made the oxo        glycol composition in step c), and the recycle content value is        based at least partly on the amount of recycle content contained        in the r-olefin or r-aldehyde.

In another more detailed direct method, a recycle content can beintroduced or established in oxo glycol by:

-   -   a. making a recycle olefin composition (e.g., propylene) at        least a portion of which is directly derived from the pyrolysis        of recycle waste or from cracking r-pyoil or obtained from        r-pygas (“dr-olefin”);    -   b. making aldehyde with a feedstock containing dr-olefin        (“dr-aldehyde”);    -   c. designating at least a portion of the olefin or aldehyde as        containing a recycle content corresponding to at least a portion        of the amount of dr-olefin or dr-aldehyde contained in the        feedstock to obtain a dr-olefin or dr-aldehyde,    -   d. making an oxo glycol with a feedstock containing dr-olefin or        dr-aldehyde,    -   e. designating at least a portion of the oxo glycol as        containing a recycle content corresponding to at least a portion        of the amount of dr-olefin or dr-aldehyde contained in the        feedstock to obtain a dr-oxo glycol,    -   f. and optionally offering to sell or selling the dr-oxo glycol        as containing or obtained with recycle content corresponding        with such designation.

In these direct methods, the r-olefin or r-aldehyde content used to makethe oxo glycol would be traceable to the olefin or aldehyde made by asupplier by cracking r-pyoil or obtained from r-pygas. Not all of theamount of r-olefin or r-aldehyde used to make the olefin or aldehydeneed be designated or associated with the olefin or aldehyde. Forexample, if 1000 kg of r-olefin or r-aldehyde is used to make r-oxoglycol, the olefin or aldehyde manufacturer can designate less than 1000kg of recycle content toward a particular batch of feedstock used tomake the olefin or aldehyde and may instead spread out the 1000 kgrecycle content amount over various productions runs to make olefin oraldehyde. The olefin or aldehyde manufacturer may elect to offer forsale its dr-oxo glycol and in doing so may also elect to represent ther-oxo glycol that is sold as containing, or obtained with sources thatcontain, a recycle content.

There is also provided a use for an olefin or aldehyde derived directlyor indirectly from cracking r-pyoil or obtained from r-pygas, the useincluding converting r-olefin or r-aldehyde in any synthetic process tomake oxo glycols.

There is also provided a use for an r-olefin or r-aldehyde allotment oran r-olefin or r-aldehyde allotment that includes converting an olefinor aldehyde in a synthetic process to make oxo glycols and applying atleast a portion of an r-olefin or r-aldehyde allotment or the r-olefinor r-aldehyde allotment to the oxo glycol. An r-olefin or r-aldehydeallotment or an r-olefin or r-aldehyde allotment is an allotment that iscreated by pyrolyzing recycled waste. Desirably, the allotmentsoriginate from the cracking of r-pyoil, or cracking of r-pyoil in a gasfurnace, or from r-pygas.

There is also provided a use for an oxo glycol formed byhydroformylating olefin to form an aldehyde, and then further reactingthe aldehyde to form the oxo glycol, either by further condensation withformaldehyde or by hydrogenation, and applying at least a portion of arecycle content allotment to at least a portion of the oxo glycol tomake an r-oxo glycol. At least a portion of the recycle inventory fromwhich the recycle content allotment is applied to the oxo glycol areallotments originating from pyrolyzing recycled waste. Desirably, theallotments originate from the cracking of r-pyoil, or cracking ofr-pyoil in a gas furnace, or from r-pygas. Also, the allotment appliedto the oxo glycol can be a recycle content allotment originating frompyrolyzing recycled waste.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a use of a recycle inventory byconverting any olefin or aldehyde composition in a synthetic process tomake an oxo glycol composition (“oxo glycol”); deducting a recyclecontent value from the recycle inventory and applying at least a portionof the deducted recycle content value to the oxo glycol, and at least aportion of the inventory contains a recycle content allotment. Therecycle content allotment can be present in the inventory at the time ofdeducting a recycle content value from the recycle inventory, or arecycle content allotment deposit is made into the recycle inventorybefore deducting a recycle content value (but need not be present oraccounted for when a deduction is made), or it can be present within ayear from the deduction, or within the same calendar year as thededuction, or within the same month as the deduction, or within the sameweek as the deduction. In one embodiment or in combination with any ofthe mentioned embodiments, the recycle content deduction is withdrawnagainst a recycle content allotment.

In one embodiment or in combination with any of the mentionedembodiments, there is provided an oxo glycol composition that isobtained by any of the methods described above. The same operator,owner, of Family of Entities may practice each of these steps, or one ormore steps may be practiced among different operators, owners, or Familyof Entities.

The olefin or aldehyde can be stored in a storage vessel and transferredto an oxo glycol manufacturing facility by way of truck, pipe, or ship,or as further described below, the olefin or aldehyde productionfacility can be integrated with the oxo glycol facility. The olefin oraldehyde may be shipped or transferred to the operator or facility thatmakes the oxo glycol.

In one embodiment or in combination with any of the mentionedembodiments, one may integrate two or more facilities and make r-oxoglycol. The facilities to make r-oxo glycol, the r-olefin or r-aldehyde,and the r-pyoil and/or r-pygas, can be stand-alone facilities orfacilities integrated to each other. For example, one may establish asystem of producing and consuming a recycle olefin or aldehydecomposition at least a portion of which is obtained from directly orindirectly from cracking r-pyoil or obtaining r-pygas; or a method ofmaking r-oxo glycol, as follows:

-   -   a. providing an olefin or aldehyde manufacturing facility that        produces at least in part an olefin or aldehyde composition;    -   b. providing an oxo glycol manufacturing facility that makes an        oxo glycol composition and comprising a reactor configured to        accept olefin or aldehyde; and    -   c. feeding at least a portion of said olefin or aldehyde from        the olefin or aldehyde manufacturing facility to the oxo glycol        manufacturing facility through a supply system providing fluid        communication between said facilities;        wherein any one or both of the olefin or aldehyde manufacturing        facility or oxo glycol manufacturing facility makes or supplies        an r-olefin or r-aldehyde (r-olefin or r-aldehyde) or recycle        content oxo glycol (r-oxo glycol), respectively, and optionally,        wherein the olefin or aldehyde manufacturing facility supplies        r-olefin or r-aldehyde to the oxo glycol manufacturing facility        through the supply system.

The feeding in step c) can be a supply system providing fluidcommunication between these two facilities and capable of supplying anolefin or aldehyde composition from the olefin or aldehyde manufacturingfacility to the oxo glycol manufacturing facility, such as a pipingsystem that has a continuous or discontinuous flow.

The oxo glycol manufacturing facility can make r-oxo glycol, and canmake the r-oxo glycol directly or indirectly from the pyrolysis ofrecycled waste or the cracking of r-pyoil or from r-pygas. For example,in a direct method, the oxo glycol manufacturing facility can make r-oxoglycol by accepting r-olefin or r-aldehyde from the olefin or aldehydemanufacturing facility and feeding the r-olefin or r-aldehyde as a feedstream to a reactor to make oxo glycol. Alternatively, the oxo glycolmanufacturing facility can make r-oxo glycol by accepting any olefin oraldehyde composition from the olefin or aldehyde manufacturing facilityand applying a recycle content to oxo glycol made with the olefin oraldehyde composition by deducting recycle content value from its recycleinventory and applying them to the oxo glycol, optionally in amountsusing the methods described above. The allotments obtained and stored inrecycle inventory can be obtained by any of the methods described above,and need not necessarily be allotments associated with r-olefin orr-aldehyde.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a system for producing r-oxo glycolas follows:

-   -   a. provide an olefin or aldehyde manufacturing facility        configured to produce an output composition comprising a recycle        content olefin or aldehyde (“r-olefin or r-aldehyde”);    -   b. provide an oxo glycol manufacturing facility having a reactor        configured to accept an olefin or aldehyde composition and        making an output composition comprising an r-oxo glycol; and    -   c. a supply system providing fluid communication between at        least two of these facilities and capable of supplying the        output composition of one manufacturing facility to another one        or more of said manufacturing facilities.

The oxo glycol manufacturing facility can make r-oxo glycol, and canmake the r-oxo glycol directly or indirectly from the pyrolysis ofrecycled waste. In this system, the olefin or aldehyde manufacturingfacility can have its output in fluid communication with the olefin oraldehyde manufacturing facility which in turn can have its output influid communication with the oxo glycol manufacturing facility.Alternatively, the manufacturing facilities of a) and b) alone can be influid communication. In the latter case, the oxo glycol manufacturingfacility can make r-oxo glycol directly by having the r-olefin orr-aldehyde or r-olefin or r-aldehyde produced in the olefin or aldehydemanufacturing facility converted all the way to oxo glycol, orindirectly by accepting any olefin or aldehyde composition from theolefin or aldehyde manufacturing facility and applying a recycle contentto oxo glycol by deducting allotments from its recycle inventory andapplying them to the oxo glycol, optionally in amounts using the methodsdescribed above. The allotments obtained and stored in recycle inventorycan be obtained by any of the methods described above, and need notnecessarily be allotments associated with r-olefin or r-aldehyde. Forexample, the allotments can be obtained from any facility or source, solong as they originate from the pyrolysis of recycled waste, or thecracking r-pyoil or obtained from r-pygas.

The fluid communication can be gaseous, or liquid if compressed. Thefluid communication need not be continuous and can be interrupted bystorage tanks, valves, or other purification or treatment facilities, solong as the fluid can be transported from one facility to the subsequentfacility through, for example, an interconnecting pipe network andwithout the use of truck, train, ship, or airplane. For example, one ormore storage vessels may be placed in the supply system so that ther-olefin or r-aldehyde facility feeds r-olefin or r-aldehyde to astorage facility and r-olefin or r-aldehyde can be withdrawn from thestorage facility as needed by the oxo glycol manufacturing facility,with valving and pumps and compressors utilized an in line with thepiping network as needed. Further, the facilities may share the samesite, or in other words, one site may contain two or more of thefacilities. Additionally, the facilities may also share storage tanksites, or storage tanks for ancillary chemicals, or may also shareutilities, steam or other heat sources, etc., yet also be considered asdiscrete facilities since their unit operations are separate. A facilitywill typically be bounded by a battery limit.

In one embodiment or in combination with any of the mentionedembodiments, the integrated process includes at least two facilitiesco-located within 5, or within 3, or within 2, or within 1 mile of eachother (measured as a straight line). In one embodiment or in combinationwith any of the mentioned embodiments, at least two facilities are ownedby the same Family of Entities.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided an integrated r-olefin or r-aldehydeand r-oxo glycol generating and consumption system. This systemincludes:

-   -   a. provide an olefin or aldehyde manufacturing facility        configured to produce an output composition comprising a recycle        content olefin or aldehyde (“r-olefin or r-aldehyde”);    -   b. provide oxo glycols manufacturing facility having a reactor        configured to accept an olefin or aldehyde composition and        making an output composition comprising an r-oxo glycol; and    -   c. a piping system interconnecting at least two of said        facilities, optionally with intermediate processing equipment or        storage facilities, capable of taking off the output composition        from one facility and accept said output at any one or more of        the other facilities.

The system does not necessarily require a fluid communication betweenthe two facilities, although fluid communication is desirable. In thissystem, olefin or aldehyde or olefin or aldehyde made at the olefin oraldehyde manufacturing facility can be delivered to the olefin oraldehyde facility through the interconnecting piping network that can beinterrupted by other processing equipment, such as treatment,purification, pumps, compression, or equipment adapted to combinestreams, or storage facilities, all containing optional metering,valving, or interlock equipment. The equipment can be a fixed to theground or fixed to structures that are fixed to the ground. Theinterconnecting piping does not need to connect to the olefin oraldehyde reactor or the cracker, but rather to a delivery and receivingpoint at the respective facilities. The same concept applies between theolefin or aldehyde facility and the oxo glycol facility. Theinterconnecting pipework need not connect all three facilities to eachother, but rather the interconnecting pipework can be between facilitiesa)-b), or b)-c), or between a)-b)-c).

There can now also be provided a package or a combination of an r-oxoglycol and a recycle content identifier associated with r-oxo glycol,where the identifier is or contains a representation that the oxo glycolcontains, or is sourced from or associated with a recycle content. Thepackage can be any suitable package for containing an oxo glycol, suchas a plastic or metal drum, railroad car, isotainer, totes, polytotes,IBC totes, bottles, jerricans, and polybags.

The identifier can be a certificate document, a product specificationstating the recycle content, a label, a logo or certification mark froma certification agency representing that the article or package containscontents or the oxo glycol contains, or is made from sources orassociated with recycle content, or it can be electronic statements bythe oxo glycol manufacturer that accompany a purchase order or theproduct, or posted on a website as a statement, representation, or alogo representing that the oxo glycol contains or is made from sourcesthat are associated with or contain recycle content, or it can be anadvertisement transmitted electronically, by or in a website, by email,or by television, or through a tradeshow, in each case that isassociated with oxo glycol. The identifier need not state or representthat the recycle content is derived directly or indirectly from crackingr-pyoil or obtained from r-pygas. Rather, it is sufficient that the oxoglycol is directly or indirectly obtained at least in part from thecracking of r-pyoil, and the identifier can merely convey or communicatethat the oxo glycol has or is sourced from a recycle content, regardlessof the source.

In one embodiment or in combination with any of the mentionedembodiments, there is provided a system or package comprising:

-   -   a. oxo glycol (“oxo glycol”), and    -   b. an identifier (e.g. a credit, label or certification)        associated with said oxo glycol, said identifier being a        representation that said oxo glycol has recycle content or is        made from a source having recycle content.

The system can be a physical combination, such as package having atleast oxo glycol as its contents and the package has a label, such as alogo, that the contents such as the oxo glycol has or is sourced from arecycle content. Alternatively, the label or certification can be issuedto a third party or customer as part of a standard operating procedureof an entity whenever it transfers or sells oxo glycol having or sourcedfrom recycle content. The identifier does not have to be physically onthe oxo glycol or on a package, and does not have to be on any physicaldocument that accompanies or is associated with the oxo glycol. Forexample, the identifier can be an electronic credit or certification orrepresentation transferred electronically by the oxo glycol manufacturerto a customer in connection with the sale or transfer of the oxo glycolproduct, and by sole virtue of being a credit, it is a representationthat the oxo glycol has recycle content. The identifier, such as a label(such as a logo) or certification need not state or represent that therecycle content is derived directly or indirectly from cracking r-pyoilor obtained from r-pygas.

Rather, it is sufficient that the oxo glycol is directly or indirectlyobtained at least in part either (i) from pyrolyzing recycled waste or(ii) from a recycle inventory into which at least a portion of thedeposits or credits in the recycle inventory have their origin inpyrolyzing recycled waste. The identifier itself need only convey orcommunicate that the oxo glycol has or is sourced from a recyclecontent, regardless of the source. In one embodiment or in combinationwith any of the mentioned embodiments, articles made from the oxo glycolmay have the identifier, such as a stamp or logo embedded or adhered tothe article. In one embodiment or in combination with any of thementioned embodiments, the identifier is an electronic recycle contentcredit from any source. In one embodiment or in combination with any ofthe mentioned embodiments, the identifier is an electronic recyclecontent credit derived directly or indirectly from pyrolyzing recycledwaste.

In one embodiment or in combination with any of the mentionedembodiments, the r-oxo glycol, or articles made thereby, can be offeredfor sale or sold as oxo glycol containing or obtained with, or anarticle containing or obtained with, recycle content. The sale or offerfor sale can be accompanied with a certification or representation ofthe recycle content claim made in association with the oxo glycol orarticle made with the oxo glycol.

The obtaining of an allocation and designating (whether internally suchas through a bookkeeping or a recycle inventory tracking softwareprogram or externally by way of declaration, certification, advertising,representing, etc.) can be by the oxo glycol manufacturer or within theoxo glycol manufacturer Family of Entities. The designation of at leasta portion of the oxo glycol as corresponding to at least a portion ofthe allotment (e.g. allocation or credit) can occur through a variety ofmeans and according to the system employed by the oxo glycolmanufacturer, which can vary from manufacturer to manufacturer. Forexample, the designation can occur internally merely through a log entryin the books or files of the oxo glycol manufacturer or other inventorysoftware program, or through an advertisement or statement on aspecification, on a package, on the product, by way of a logo associatedwith the product, by way of a certification declaration sheet associatedwith a product sold, or through formulas that compute the amountdeducted from recycle inventory relative to the amount of recyclecontent applied to a product.

Optionally, the oxo glycol can be sold. In one embodiment or incombination with any of the mentioned embodiments, there is provided amethod of offering to sell or selling oxo glycols by:

-   -   a. converting an olefin or aldehyde composition in a synthetic        process to make oxo glycol composition (“oxo glycol”),    -   b. applying a recycle content value to at least a portion of the        oxo glycol to thereby obtain a recycle oxo glycol (“r-oxo        glycol”), and    -   c. offering to sell or selling the r-oxo glycol as having a        recycle content or obtained or derived from recycled waste.

An oxo glycol manufacturer or its Family of Entities can obtain arecycle content allocation, and the allocation can be obtained by any ofthe means described herein and can be deposited into recycle inventory,the recycle content allocation derived directly or indirectly from thepyrolysis of recycled waste. The olefin or aldehyde converted in asynthetic process to make an oxo glycol composition can be any olefin oraldehyde composition obtained from any source, including a non-r-olefinor r-aldehyde composition, or it can be an r-olefin or r-aldehydecomposition. The r-oxo glycol sold or offered for sale can be designated(e.g. labelled or certified or otherwise associated) as having a recyclecontent value. In one embodiment or in combination with any of thementioned embodiments, at least a portion of the recycle content valueassociated with the r-oxo glycol can be drawn from a recycle inventory.In another embodiment, at least a portion of the recycle content valuein the oxo glycol is obtained by converting r-olefin or r-aldehyde. Therecycle content value deducted from the recycle inventory can be anon-pyrolysis recycle content value or can be a pyrolysis recyclecontent allocation; i.e. a recycle content value that has its origin inpyrolysis of recycled waste.

The recycle inventory can optionally contain at least one entry that isan allocation derived directly or indirectly from pyrolysis of recycledwaste. The designation can be the amount of allocation deducted fromrecycle inventory, or the amount of recycle content declared ordetermined by the oxo glycol manufacturer in its accounts. The amount ofrecycle content does not necessarily have to be applied to the oxoglycol product in a physical fashion. The designation can be an internaldesignation to or by the oxo glycol manufacturer or its Family ofEntities or a service provider in contractual relationship to the oxoglycol manufacturer or its Family of Entities. The amount of recyclecontent represented as contained in the oxo glycol sold or offered forsale has a relationship or linkage to the designation. The amount ofrecycle content can be a 1:1 relationship in the amount of recyclecontent declared on an oxo glycol offered for sale or sold and theamount of recycle content assigned or designated to the oxo glycol bythe oxo glycol manufacturer.

The steps described need not be sequential, and can be independent fromeach other. For example, the steps a) and b) can be simultaneous, suchas would be the case if employs an r-olefin or r-aldehyde composition tomake the oxo glycol since the r-olefin or r-aldehyde is both an olefinor aldehyde composition and has a recycle content allocation associatedwith it; or where the process of making oxo glycol is continuous and theapplication of the oxo glycol application of the recycle content valueoccurs during the manufacture of oxo glycol.

Process for Making Oxo Glycols

Oxo glycols are formed by reacting aldehydes formed by hydroformylationof olefins to provide multifunctional alcohols. One example of an oxoglycol is 2,2-dimethyl-1,3-propanediol, which is also called neopentylglycol or NPG. NPG is a chemical component useful as a solvent and/or anintermediate in forming a range of other compounds including, forexample, plasticizers, polyesters, paints, lubricants, and others. Incertain embodiments, NPG may be formed via aldol condensation ofisobutyraldehyde and formaldehyde followed by the hydrogenation of theintermediate aldehyde (2,2-dimethyl-3-hydroxy propanal) or by furthercondensation of the intermediate aldehyde in the presence of excessformaldehyde. The isobutyraldehyde may be formed via hydroformylation ofpropylene with syngas (hydrogen and carbon monoxide), and at least aportion of the propylene may comprise recycle content propylene(r-propylene) as discussed in detail herein. As a result, one or more ofthe intermediate (isobutyraldehyde and/or 2,2-dimethyl-3-hydroxypropanal) or final product (NPG) may comprise recycle contentintermediates (r-isobutyraldehyde and/or r-2,2-dimethyl-3-hydroxypropanal) or recycle content products (r-NPG).

FIG. 26 shows a system suitable for forming a recycle content neopentylglycol (r-NPG) from recycle content propylene (r-propylene) is provided.As depicted in FIG. 26, the system suitable for forming a recyclecontent neopentyl glycol (r-NPG) from recycle content propylene(r-propylene) may include the following components: (1) a pyrolysisunit/facility configured to i) pyrolyze a pyrolysis feed comprising arecycled waste material and ii) produce a pyrolysis effluent comprisinga recycle content pyrolysis oil composition (r-pyoil) and optionallyrecycle content pyrolysis gas (r-pygas); (2) a cracking unit/facilityconfigured to i) crack a cracker feed stream comprising at least aportion of the r-pyoil and ii) produce a cracker effluent; (3) aseparation unit/facility downstream of and in fluid communication withthe cracking unit/facility for separating at least a portion of thecracker effluent into one or more product streams including, forexample, a stream comprising a recycle content propylene composition(r-propylene); (4) a hydroformylation unit/facility configured to i)react at least a portion of the r-propylene with syngas comprisingcarbon monoxide (CO) and hydrogen (H₂) and ii) produce ahydroformylation effluent comprising recycle content aldehyde(r-aldehyde); and (5) a condensation unit/facility for reactingaliphatic aldehydes comprising r-aldehyde to form a longer-chainaldehyde intermediate or a glycol; and (6) optionally, a hydrogenationunit/facility for hydrogenating the aldehyde intermediate to form aglycol, which can include a recycle content glycol.

The pyrolysis units and cracking units shown in FIG. 26 may includethose, or components of those, that were previously described herein. Incertain embodiments, the pyrolysis unit/facility, the crackingunit/facility, the hydroformylation unit/facility, and/or thecondensation unit/facility may be in fluid communication. In some cases,the pyrolysis unit and cracking unit may be separately located and/oroperated, while, in other cases, the pyrolysis and cracking units may beco-located as described herein. Similarly, the pyrolysis and/or crackingunits may be separately located and/or operated, or co-located, with thehydroformylation, condensation, and/or hydrogenation unit/facility.

As shown in FIG. 26, a stream comprising r-olefin may be routed from theseparation zone/unit of the cracking unit/facility to a hydroformylationunit. Hydroformylation is a process used to produce aldehydes byreacting a starting alkene with syngas (e.g., carbon monoxide andhydrogen) in the presence of a catalyst. The resulting aldehydes can beshort, medium or long chain aldehydes and can, for example, includebetween 3 and 30 carbon atoms per molecule, depending on the specificstarting alkenes (olefins). Typically, the starting alkenes include oneless carbon atom per molecule than the final aldehyde and can, forexample, include between 2 and 29 carbon atoms per molecule. In anembodiment or in combination with any of the embodiments mentionedherein, at least a portion of the starting alkene used in ahydroformylation reaction may be a recycle content alkene (r-alkene). Asused herein, the terms “alkene” and “olefin” are interchangeable. Thus,examples of r-alkenes suitable for use in the hydroformylation reactioninclude r-ethylene, r-butylene, and r-propylene.

In an embodiment or in combination with any of the embodiments mentionedherein, at least 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 percent ofthe total weight of the hydroformylation feed stream can compriseolefin, including r-olefin such as r-propylene. In some cases, ther-olefin can comprise, consist essentially of, or consist ofr-propylene, or the total amount of r-olefin may include at least about20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 weightpercent of r-propylene, based on the total weight or r-olefin in thefeed stream. The total amount of r-olefin in the feed stream to thehydroformylation unit can be at least 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, 85, 90, or 95 weight percent, based on the totalweight of the hydroformylation feed stream. Additionally oralternatively, in certain embodiments, the feed stream going into thehydroformylation reactor may comprise not more than 99, 95, 90, 85, 80,75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 weightpercent of the r-propylene.

In certain embodiments, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 percent of the total amount ofpropylene fed into the hydroformylation zone comprises r-propylene, withthe balance (if any) being non-recycle content propylene. In certainembodiments, the feed stream going into the hydroformylation reactor maycomprise an propylene to r-propylene weight ratio of at least 0.1:1,0.5:1, 1:1, 2:1, 3:1, or 4:1. Additionally or alternatively, in certainembodiments, the feed going into the hydroformylation reactor maycomprise an propylene to r-propylene weight ratio of not more than100:1, 50:1, 25:1, 10:1, 5:1, 4:1, 3:1, 2:1, 1:1, 0.5:1, or 0.1:1.

The propylene (including r-propylene) may be reacted with syngas in thepresence of a catalyst in a hydroformylation reactor within thehydroformylation zone. In an embodiment or in combination with any ofthe embodiments mentioned herein, the syngas stream introduced into thehydroformylation reactor can comprise at least 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, or 70 and/or not more than 90, 85, 80, 75,70, 65, 60, 55, 50, or 45 weight percent of hydrogen and/or carbonmonoxide. The molar ratio of carbon monoxide to hydrogen can be at least0.5:1, 0.75:1, 1:1, 1.25:1 or 1.5:1 and/or not more than 5:1, 3.5:1,2.5:1, 2:1, 1.75:1, 1.5:1 or 1:1. The syngas stream may include at least1, 2, 5, 10, or 15 and/or not more than 45, 40, 35, 30, 25, 20, 15, or10 weight percent of one or more other components, such as, for example,carbon dioxide, based on the total weight of the stream.

Although it is not essential, an inert solvent can be employed as ahydroformylation reaction medium diluent. A variety of solvents can beused, including ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone, acetophenone, and cyclohexanone; aromatics such asbenzene, toluene and xylenes; halogenated aromatics includingorthodichlorobenzene; ethers such as tetrahydrofuran, dimethoxyethaneand dioxane; halogenated paraffins including methylene chloride;paraffinic hydrocarbons such as heptane; or combinations thereof.

As shown in FIG. 26, the hydroformylation reaction also takes place inthe presence of a catalyst. The catalyst used in the hydroformylationreaction can be a transition metal catalyst such as, for example, acomplexed rhodium or cobalt catalyst. The specific catalyst depends, inpart, on the specific type of hydroformylation being conducted. Ligandsused to complex the metal may include, for example, phosphorous-basedligands such as phosphine or phosphane ligands. Specific examplesinclude, but are not limited to, triphenylphosphines,triphenylphosphanes, and combinations thereof. Other examples ofsuitable ligands can include, for example, carbonyl-based ligands, whichare predominantly used with cobalt. The catalyst may be homogeneous and,optionally, water soluble. Most hydroformylation units/facilitiesinclude one or more catalyst separation units for recovery and recycleof at least a portion of the catalyst to the hydroformylation reactor.

In certain embodiments, the hydroformylation process may occur at atemperature in the range of 40 to 200° C., 50 to 150° C., or 60 to 120°C., or even 80 to 105° C. In certain embodiments, the hydroformylationprocess may occur at a pressure in the range of 0.01 to 35 MPa, 0.1 to12 MPa, or 1 to 7 MPa.

Additionally, the hydroformylation unit/facility may further include oneor more separators (not shown) for purifying the effluent streamwithdrawn from the hydroformylation reactor. The separators may beconfigured to separate catalyst from the reactor effluent or to separatethe aldehydes to form streams of purified aldehydes. For example, incertain embodiments, the effluent stream from the hydroformylationreactor may comprise at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, or 95 and/or not more than 99, 95, 90, 85, 80, 75,70, 65, or 60 weight percent of C4 aldehydes such as, for example,normal and isobutyl aldehydes.

In some cases, the amount of isobutyl aldehyde (i-butyraldehyde) can beat least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 percentand/or not more than 99, 95, 90, 85, 80, 75, 70, 65, or 60 percent ofthe total amount of C4 aldehydes present in the reactor effluent streamwith the balance being, for example, normal butyraldehyde. Theseparators, when present in the hydroformylation facility, may be usedto separate the C4 aldehyde isomers from one another so that, forexample, the product stream withdrawn from the hydroformylationunit/facility can be at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,97, or 99 weight percent of isobutyraldehyde, based on the total weightof the C4 aldehydes in the stream. Of that, at least a portion, or all,can comprise recycle content isobutyraldehyde (r-isobutyraldehyde).Similar separations may be performed to provide similar streams ofnormal butyraldehyde, including r-normal butyraldehyde.

Various hydroformylation processes and systems are described in U.S.Pat. Nos. 2,464,916; 4,148,830; 5,264,600; 4,593,127; 7,935,850;7,420,092; 6,492,564; 4,625,068; 4,169,861; 3,448,157; European PatentNo. 0804398; and U.S. Pat. No. 7,049,473, the entire disclosures areincorporated herein by reference to the extent not inconsistent with thepresent disclosure.

The resulting r-aldehyde may comprise at least one pyoil-derivedimpurity derived from the r-propylene or other recycle contentintermediates used to form the r-NPG. In certain embodiments, ther-aldehyde may comprise at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 ppmand/or not more than 1,000, 900, 800, 700, 600, 500, 400, 300, 200, or100 ppm of at least one pyoil-derived impurity derived from ther-propylene.

As shown in FIG. 26, the effluent from the hydroformylation unit, whichcan include, in certain embodiments, at least about 50, 55, 60, 65, 70,75, 80, 85, 90, or 95 weight percent of isobutyraldehyde, based on thetotal amount of aldehyde in the stream, can be passed into acondensation facility/unit. In an embodiment or in combination with anyof the embodiments mentioned herein, at least 50, 55, 60, 65, 70, 75,80, 85, 90, or 95 percent of the total weight of the feed to thecondensation unit/facility can include an aldehyde, including r-aldehydesuch as r-butyraldehyde or, in particular, r-isobutyraldehyde. In somecases, the r-butyraldehyde can comprise, consist essentially of, orconsist of r-isobutyraldehyde, or the total amount of r-butyraldehyde(or r-isobutyraldehyde) may include at least about 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 weight percent ofr-butyraldehyde (or r-isobutyraldehyde), based on the total weight orr-aldehyde in the feed stream to the aldol condensation unit/facility.

The total amount of r-aldehyde (or r-butyraldehyde orr-isobutyraldehyde) in the feed stream to the aldol condensation unitcan be at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, or 95 weight percent, based on the total weight of the aldolcondensation feed stream. Additionally or alternatively, in certainembodiments, the feed stream going into the aldol condensation reactormay comprise not more than 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50,45, 40, 35, 30, 25, 20, 15, 10, 5, or 1 weight percent of r-aldehyde,r-butyraldehyde, or r-isobutyraldehyde.

In certain embodiments, at least 5, 10, 15, 02, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 percent of the total amount ofaldehyde (or butyraldehyde) fed into the condensation zone comprisesr-butyraldehyde (or r-isobutyraldehyde), with the balance (if any) beingnon-recycle content butyraldehyde (or isobutyraldehyde). In certainembodiments, the feed stream going into the aldol condensation reactormay comprise a butyraldehyde to r-butyraldehyde (or isobutyraldehyde tor-isobutyraldehyde) weight ratio of at least 0.1:1, 0.5:1, 1:1, 2:1,3:1, or 4:1. Additionally or alternatively, in certain embodiments, thefeed going into the aldol condensation reactor may comprise an abutyraldehyde to r-butyraldehyde (or isobutyraldehyde tor-isobutyraldehyde) weight ratio of not more than 100:1, 50:1, 25:1,10:1, 5:1, 4:1, 3:1, 2:1, 1:1, 0.5:1, or 0.1:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the effluent from the hydroformylation reaction may include amixture of n-butyraldehyde and i-butyraldehyde, which it may bedesirable to separate. For example, the effluent stream may include atleast 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 weight percent and/ornot more than 90, 85, 80, 75, 70, 65, 60, 55, 50, or 45 weight percentof n-butyraldehyde or of i-butyraldehyde. Thus, the effluent from thehydroformylation reactor may be passed through one or more separationcolumns (such as, for example, multi-stage distillation columns) toseparate the i-butyraldehyde from the n-butyraldehyde. In some cases,the purified streams of n-butyraldehyde and i-butyraldehyde can includeat least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, or 99 percent byweight of i-butyraldehyde or n-butyraldehyde, respectively.

In the condensation reactor or unit/facility, the isobutyraldehyde canreact with formaldehyde in the presence of a catalyst to formhydroxypivaldehyde (2,2-dimethyl-3-hydroxypropanal). The streamproviding formaldehyde to the condensation reactor or unit/facility mayinclude at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,or 80 weight percent and/or not more than 100, 95, 90, 85, 80, 75, 70,65, 60, or 55 weight percent formaldehyde based on the total weight ofthe formaldehyde-containing stream. The molar ratio of isobutyraldehydeto formaldehyde (or r-isobutyraldehyde to formaldehyde) in thecondensation reactor (or in the feed streams introduced into thereactor) can be at least 0.75:1, 0.8:1, 0.85:1, 0.90:1, 0.95:1, 1:1,1.1:1 and/or not more than 1.4:1, 1.35:1, 1.3:1, 1.25:1, 1.2:1, 1.15:1,or 1.1:1.

The aldehyde fed into the aldol condensation reactor may be condensed inthe presence of a catalyst. The catalyst may be any type of catalystsuitable for such reactions and can comprise, for example, a basiccatalyst. Suitable catalysts can include, but are not limited to, alkalimetal oxides or hydroxides, alkaline earth metal hydroxides andcombinations thereof. Examples of specific catalyst types can includesodium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide,and combinations and solutions thereof. The catalyst may be homogenousor heterogeneous and can be present in the reaction medium in an amountof at least 0.1, 0.5, 0.75, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6weight percent and/or not more than 15, 12, 10, 8, 6, 5, 4, 3.5, 3, 2.5,2, 1.5, 1, or 0.5 weight percent, based on the total weight of thereaction mixture.

Although not required, the condensation reaction may be carried out inthe presence of a solvent. The solvent may be present in the reactionmedium in an amount of at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,or 60 and/or not more than 85, 80, 75, 70, 65, 60, 55, 50, or 45 weightpercent, based on the total weight of the reaction medium. Examples ofsuitable solvents can include, but are not limited to, methanol,ethanol, n-propanol, iso-propanol, iso-butanol, and combinationsthereof. In some embodiments, the solvent can be an aqueous solvent.

The condensation reaction may be carried out at a temperature of atleast 35, 40, 45, 50, 55, or 60° C. and/or not more than 125, 120, 115,110, 105, 100, 95, 90, 85, 80, 75, 70 or 65° C., for a period of atleast 15, 30 minutes, 1 hour, or 1.5 hours and/or not more than 5, 4, 3,or 2.5 hours. Alternatively, the reaction time can be at least 1, 2, 3,4, 5, 6, or 7 minutes and/or not more than 20, 18, 16, 12, 10, 8, 6, or5 minutes. The pressure of the reaction may be near, slightly above orslightly below atmospheric.

The resulting hydroxypivaldehyde intermediate can comprise recyclecontent such that, for example, at least 5, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 and/or not more than 99, 95,90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, or 35 weight percent ofrecycle content hydroxypivaldehyde (r-hydroxypivaldehyde).

As shown in FIG. 26, at least a portion of the effluent stream withdrawnfrom the condensation unit/facility can optionally be fed into ahydrogenation unit, wherein the hydroxypivaldehyde (orr-hydroxypivaldehyde) can be hydrogenated to form2,2-dimethyl-1,3-propanediol (or neopentyl glycol). In certainembodiments, the ratio of hydrogen to hydroxypivaldehyde fed into thehydrogenation reactor can be at least 0.5:1, 0.75:1, 0.8:1, 0.9:1, 1:1,1.2:1, 1.5:1, 2:1 and/or not more than 4:1, 3.5:1, 3:1, 2.5:1, 2:1,1.5:1, or 1:1.

The hydrogenation reaction can be performed in the presence of acatalyst. Examples of suitable catalysts can include, but are notlimited to, catalysts comprising metals such as platinum, ruthenium,tungsten, copper, cobalt, molybdenum, palladium, and combinationsthereof. The catalyst may be a heterogeneous catalyst and can besupported on a catalyst support. Suitable types of catalyst support caninclude, but are not limited to, silica, alumina, silica-alumina,zeolites, magnesium oxide, titanium oxide, zirconium oxide, diatomaceousearth, carbon, silicon carbide, and combinations thereof. Whensupported, the catalytic metal may be present in an amount of at least0.1, 0.5, 0.75, 1, 1.5, 2, 2.5, or 3 and/or not more than 10, 8, 6, 5,4, 3, or 2 weight percent, based on the total weight of the catalyst.

The resulting product stream withdrawn from the hydrogenation reactor orunit/facility can include at least 5, 10, 15, 20, 25, 30, 35, 40, 45,50, 55, 60, 65, 70, 75, 80, or 85 weight percent and/or not more than99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 weightpercent of neopentyl glycol, based on the total weight of the steam. Ofthe total amount of neopentyl glycol in the effluent stream, at least 5,10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,or all and/or not more than 100, 99, 95, 90, 85, 80, 75, 70, 65, 60, 55,50, 45, 40, 35, 30, 25, or 20 weight percent of the neopentyl glycol maycomprise recycle content neopentyl glycol (r-NPG).

Alternatively, the neopentyl glycol can be formed by further reactingthe hydroxypivaldehyde (or r-hydroxypivaldehyde) with an excess offormaldehyde in the Aldol condensation reactor. For example, the molarratio of formaldehyde to hydroxypivaldehyde (or r-hydroxypivaldehyde)can be at least about 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1,1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1 and/or not morethan 5:1, 4.5:1, 4:1, 3.5:1, 3:1, or 2.5:1. The resulting product streamwithdrawn from the reactor or unit/facility can include at least 5, 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weightpercent and/or not more than 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50,45, 40, 35, 30, or 25 weight percent of neopentyl glycol, based on thetotal weight of the steam. Of the total amount of neopentyl glycol inthe effluent stream, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, 85, 90, 95, or all and/or not more than 100, 99, 95,90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20 weightpercent of the neopentyl glycol may comprise recycle content neopentylglycol (r-NPG).

Various condensation processes and systems used to form neopentyl glycoland similar components are described in U.S. Pat. Nos. 1,048,530,1,219,162, 3,920,760, 4,021,496, West German Patent No. 1,014,089; U.S.Pat. Nos. 4,933,473; and 3,340,312, the entire disclosures of which areincorporated herein by reference to the extent not inconsistent with thepresent disclosure.

The resulting product or effluent stream comprising r-neopentyl glycolmay comprise at least one pyoil-derived impurity derived from ther-propylene. In certain embodiments, the r-neopentyl glycol may compriseat least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 ppm and/or not more than1,000, 900, 800, 700, 600, 500, 400, 300, 200, or 100 ppm of at leastone pyoil-derived impurity derived from the r-propylene.

EXAMPLES r-Pyoil Examples 1-4

Table 1 shows the composition of r-pyoil samples by gas chromatography.The r-pyoil samples produced the material from waste high and lowdensity polyethylene, polypropylene, and polystyrene. Sample 4 was alab-distilled sample in which hydrocarbons greater than C21 wereremoved. The boiling point curves of these materials are shown in FIGS.13-16.

TABLE 1 Gas Chromatography Analysis of r-Pyoil Examples r-Pyoil FeedExamples Components 1 2 3 4 Propene 0.00 0.00 0.00 0.00 Propane 0.000.19 0.20 0.00 1,3-Butadiene 0.00 0.93 0.99 0.31 Pentene 0.16 0.37 0.390.32 Pentane 1.81 3.21 3.34 3.05 1,3-cyclopentadiene 0.00 0.00 0.00 0.002-methyl-Pentene 1.53 2.11 2.16 2.25 2-methyl-Pentane 2.04 2.44 2.483.03 Hexane 1.37 1.80 1.83 2.10 2-methyl-1,3-cyclopentadiene 0.00 0.000.00 0.00 1-methyl-1,3-cyclopentadiene 0.00 0.00 0.00 0.00 2,4dimethylpentene 0.32 0.18 0.18 0.14 Benzene 0.00 0.16 0.16 0.005-methyl-1,3-cyclopentadiene 0.00 0.17 0.17 0.20 Heptene 1.08 1.15 1.151.55 Heptane 2.51 0.17 2.89 3.61 Toluene 0.58 1.05 1.09 0.844-methylheptane 1.50 1.67 1.68 1.99 Octene 1.37 1.35 1.37 1.88 Octane2.56 2.72 2.78 3.40 2,4-dimethylheptene 1.25 1.54 1.55 1.602,4-dimethylheptane 5.08 4.01 4.05 6.40 Ethylbenzene 1.85 3.10 3.12 2.52m,p-xylene 0.73 0.69 0.24 0.90 Styrene 0.40 0.13 1.13 0.53 o-xylene 0.120.36 0.00 0.00 Nonane 2.66 2.81 2.84 3.47 Nonene 1.12 0.00 0.00 1.65MW140 2.00 1.76 1.75 2.50 Cumene 0.56 0.96 0.97 0.73Decene/methylstyrene 1.29 1.17 1.18 1.60 Decane 3.14 3.23 3.25 3.90Unknown 1 0.68 0.71 0.72 0.80 Indene 0.18 0.20 0.21 0.22 Indane 0.230.34 0.26 0.26 C11 Alkene 1.50 1.32 1.33 1.77 C11 Alkane 3.30 3.30 3.333.88 C12 Alkene 1.49 1.30 0.00 0.09 Naphthalene 0.10 0.12 3.24 3.73 C12Alkane 3.34 3.21 1.31 1.66 C13 Alkane 3.20 2.90 2.97 3.40 C13 Alkene1.46 1.20 1.17 1.53 2-methylnaphthalene 0.86 0.63 0.64 0.85 C14 Alkene1.07 0.84 0.84 1.04 C14 Alkane 3.34 3.04 3.05 3.24 Acenaphthene 0.310.28 0.28 0.28 C15 Alkene 1.16 0.87 0.87 0.96 C15 Alkane 3.41 3.00 3.022.84 C16 Alkene 0.85 0.58 0.58 0.56 C16 Alkane 3.25 2.67 2.68 2.12 C17Alkene 0.70 0.46 0.46 0.35 C17 Alkane 3.04 2.43 2.44 1.50 C18 Alkene0.51 0.33 0.33 0.19 C18 Alkane 2.71 2.11 2.13 0.99 C19 Alkane 2.39 1.820.38 0.15 C19 Alkene 0.60 0.38 1.83 0.61 C20 Alkene 0.42 0.18 0.26 0.00C20 Alkane 2.05 1.55 1.55 0.37 C21 Alkene 0.31 0.00 0.00 0.00 C21 Alkane1.72 1.45 1.30 0.23 C22 Alkene 0.00 0.00 0.00 0.00 C22 Alkane 1.43 1.111.12 0.00 C23 Alkene 0.00 0.00 0.00 0.00 C23 Alkane 1.09 0.87 0.88 0.00C24 Alkene 0.00 0.00 0.00 0.00 C24 Alkane 0.82 0.72 0.72 0.00 C25 Alkene0.00 0.00 0.00 0.00 C25 Alkane 0.61 0.58 0.56 0.00 C26 Alkene 0.00 0.000.00 0.00 C26 Alkane 0.44 0.47 0.44 0.00 C27 Alkane 0.31 0.37 0.32 0.00C28 Alkane 0.22 0.29 0.23 0.00 C29 Alkane 0.16 0.22 0.15 0.00 C30 Alkane0.00 0.16 0.00 0.00 C31 Alkane 0.00 0.00 0.00 0.00 C32 Alkane 0.00 0.000.00 0.00 Unidentified 13.73 18.59 15.44 15.91 Percent C8+ 74.86 67.5067.50 66.69 Percent C15+ 28.17 22.63 22.25 10.87 Percent Aromatics 5.918.02 11.35 10.86 Percent Paraffins 59.72 54.85 54.19 51.59 Percent C4 toC7 11.41 13.72 16.86 17.40

r-Pyoil Examples 5-10

Six r-pyoil compositions were prepared by distillation of r-pyoilsamples. They were prepared by processing the material according theprocedures described below.

Example 5. r-Pyoil with at Least 90% Boiling by 350° C., 50% BoilingBetween 95° C. and 200° C., and at Least 10% Boiling by 60° C.

A 250 g sample of r-pyoil from Example 3 was distilled through a 30-trayglass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded to construct the boiling curve presented in FIG. 17. Thedistillation was repeated until approximately 635 g of material wascollected.

Example 6. r-Pyoil with at Least 90% Boiling by 150° C., 50% BoilingBetween 80° C. and 145° C., and at Least 10% Boiling by 60° C.

A 150 g sample of r-pyoil from Example 3 was distilled through a 30-trayglass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded to construct the boiling curve presented in FIG. 18. Thedistillation was repeated until approximately 200 g of material wascollected.

Example 7. r-Pyoil with at Least 90% Boiling by 350° C., at Least 10% by150° C., and 50% Boiling Between 220° C. and 280° C.

A procedure similar to Example 8 was followed with fractions collectedfrom 120° C. to 210° C. at atmospheric pressure and the remainingfractions (up to 300° C., corrected to atmospheric pressure) under 75torr vacuum to give a composition of 200 g with a boiling point curvedescribed by FIG. 19.

Example 8. r-Pyoil with 90% Boiling Between 250-300° C.

Approximately 200 g of residuals from Example 6 were distilled through a20-tray glass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. One neck of the base pot wasfitted with a rubber septum, and a low flow N2 purge was bubbled intothe base mixture by means of an 18″ long, 20-gauge steel thermometer.Batch distillation was conducted at 70 torr vacuum with a reflux rate of1:2. Temperature measurement, pressure measurement, and timer controlwere provided by a Camille Laboratory Data Collection System. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded. Overhead temperatures were corrected to atmosphericboiling point by means of the Clausius-Clapeyron Equation to constructthe boiling curve presented in FIG. 20 below. Approximately 150 g ofoverhead material was collected.

Example 9. r-Pyoil with 50% Boiling Between 60-80° C.

A procedure similar to Example 5 was followed with fractions collectedboiling between 60° C. and 230° C. to give a composition of 200 g with aboiling point curve described by FIG. 21.

Example 10. r-Pyoil with High Aromatic Content

A 250 g sample of r-pyoil with high aromatic content was distilledthrough a 30-tray glass Oldershaw column fitted with glycol chilledcondensers, thermowells containing thermometers, and a magnet operatedreflux controller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 10-20 mL, and the overhead temperatureand mass recorded to construct the boiling curve presented in FIG. 22.The distillation ceased after approximately 200 g of material werecollected. The material contains 34 weight percent aromatic content bygas chromatography analysis.

Table 2 shows the composition of Examples 5-10 by gas chromatographyanalysis.

TABLE 2 Gas Chromatography Analysis of r-Pyoil Examples 5-10. r-PyoilExamples Components 5 6 7 8 9 10 Propene 0.00 0.00 0.00 0.00 0.00 0.00Propane 0.00 0.10 0.00 0.00 0.00 0.00 1,3-r-Butadiene 0.27 1.69 0.000.00 0.00 0.18 Pentene 0.44 1.43 0.00 0.00 0.00 0.48 Pentane 3.95 4.000.00 0.00 0.37 4.59 Unknown 1 0.09 0.28 0.00 0.00 0.00 0.071,3-cyclopentadiene 0.00 0.13 0.00 0.00 0.00 0.00 2-methyl-Pentene 2.753.00 0.00 0.00 5.79 4.98 2-methyl-Pentane 2.63 6.71 0.00 0.00 9.92 5.56Hexane 0.75 4.77 0.00 0.00 11.13 3.71 2-methyl-1,3-cyclopentadiene 0.000.20 0.00 0.00 0.96 0.30 1-methyl-1,3-cyclopentadiene 0.00 0.00 0.000.00 0.00 0.00 2,4 dimethylpentene 0.00 0.35 0.00 0.00 2.06 0.26 Benzene0.00 0.24 0.00 0.00 1.11 0.26 5-methyl-1,3-cyclopentadiene 0.00 0.090.00 0.00 0.15 0.15 Heptene 0.52 5.50 0.00 0.00 6.22 2.97 Heptane 0.137.35 0.17 0.00 10.16 6.85 Toluene 1.18 2.79 0.69 0.00 2.39 6.984-methylheptane 2.54 2.46 3.29 0.00 1.16 3.92 Octene 3.09 4.72 2.50 0.000.48 2.62 Octane 5.77 6.27 3.49 0.00 0.65 4.50 2,4-dimethylheptene 3.922.30 0.61 0.00 0.96 2.58 2,4-dimethylheptane 9.47 5.80 1.30 0.00 3.740.00 Ethylbenzene 0.00 0.00 1.32 0.00 2.43 7.81 m,p-xylene 7.48 4.360.23 0.00 1.09 15.18 Styrene 0.90 1.80 0.40 0.00 2.32 1.47 o-xylene 0.280.00 0.12 0.00 0.00 0.00 Nonane 3.74 5.94 0.41 0.00 6.15 2.55 Nonene1.45 3.87 0.84 0.00 2.53 1.14 MW140 2.36 1.94 1.63 0.00 3.69 2.35 Cumene1.30 1.23 0.54 0.00 2.13 2.43 Decene/methylstyrene 1.54 1.60 1.55 0.000.30 0.48 Decane 4.31 1.68 4.34 0.00 0.48 1.08 Unknown 2 0.96 0.15 0.970.00 0.00 0.24 Indene 0.25 0.00 0.21 0.00 0.00 0.00 Indane 0.33 0.000.33 0.00 0.00 0.08 C11 Alkene 1.83 0.22 1.83 0.00 0.00 0.19 C11 Alkane4.54 0.18 4.75 0.00 0.00 0.39 C12 Alkene 1.68 0.08 2.34 0.00 0.18 0.08Naphthalene 0.09 0.00 0.11 0.00 0.00 0.00 C12 Alkane 4.28 0.09 6.14 0.000.84 0.16 C13 Alkane 4.11 0.00 6.80 3.32 0.68 0.08 C13 Alkene 1.67 0.002.85 0.38 0.37 0.00 2-methylnaphthalene 0.70 0.00 0.00 0.93 0.14 0.00C14 Alkene 0.08 0.00 1.81 3.52 0.00 0.00 C14 Alkane 0.14 0.09 6.20 14.120.00 0.00 Acenaphthylene 0.00 0.00 0.75 0.00 0.00 0.00 C15 Alkene 0.000.00 2.70 3.55 0.00 0.00 C15 Alkane 0.00 0.09 9.40 14.16 0.00 0.07 C16Alkene 0.00 0.00 1.61 2.20 0.00 0.00 C16 Alkane 0.00 0.10 5.44 12.400.00 0.00 C17 Alkene 0.00 0.00 0.10 3.35 0.00 0.00 C17 Alkane 0.00 0.100.26 16.81 0.00 0.00 C18 Alkene 0.00 0.00 0.00 0.67 0.00 0.00 C18 Alkane0.00 0.10 0.00 3.31 0.00 0.00 C19 Alkane 0.00 0.00 0.00 0.13 0.00 0.00C19 Alkene 0.00 0.00 0.00 0.00 0.00 0.00 C20 Alkene 0.00 0.00 0.00 0.000.00 0.00 C20 Alkane 0.00 0.00 0.00 0.00 0.00 0.00 C21 Alkene 0.00 0.000.00 0.00 0.00 0.00 Unidentified 18.51 16.18 21.95 21.13 19.45 13.24Percent C4-C7 12.71 38.55 0.85 0.00 50.25 37.35 Percent C8+ 68.78 45.1777.20 78.87 30.30 49.41 Percent C15+ 0.00 0.38 19.52 56.60 0.00 0.07Percent Aromatics 14.04 12.02 6.27 0.93 11.90 34.70 Percent Paraffins52.35 59.75 55.64 64.26 56.08 44.89

Examples 11-58 Involving Steam Cracking r-Pyoil in a Lab Unit

The invention is further illustrated by the following steam crackingexamples. Examples were performed in a laboratory unit to simulate theresults obtained in a commercial steam cracker. A drawing of the labsteam cracker is shown in FIG. 11. Lab Steam Cracker 910 consisted of asection of ⅜ inch Incoloy™ tubing 912 that was heated in a 24-inchApplied Test Systems three zone furnace 920. Each zone (Zone 1 922 a,Zone 2 922 b, and Zone 3 922 c) in the furnace was heated by a 7-inchsection of electrical coils. Thermocouples 924 a, 924 b, and 924 c werefastened to the external walls at the mid-point of each zone fortemperature control of the reactor. Internal reactor thermocouples 926 aand 926 b were also placed at the exit of Zone 1 and the exit of Zone 2,respectively. The r-pyoil source 930 was fed through line 980 to Iscosyringe pump 990 and fed to the reactor through line 981 a. The watersource 940 was fed through line 982 to ICSO syringe pump 992 and fed topreheater 942 through line 983 a for conversion to steam prior toentering the reactor in line 981 a with pyoil. A propane cylinder 950was attached by line 984 to mass flow controller 994. The plant nitrogensource 970 was attached by line 988 to mass flow controller 996. Thepropane or nitrogen stream was fed through line 983 a to preheater 942to facilitate even steam generation prior to entering the reactor inline 981 a. Quartz glass wool was placed in the 1 inch space between thethree zones of the furnace to reduce temperature gradients between them.In an optional configuration, the top internal thermocouple 922 a wasremoved for a few examples to feed r-pyoil either at the mid-point ofZone 1 or at the transition between Zone 1 and Zone 2 through a sectionof ⅛ inch diameter tubing. The dashed lines in FIG. 11 show the optionalconfigurations. A heavier dashed line extends the feed point to thetransition between Zone 1 and Zone 2. Steam was also optionally added atthese positions in the reactor by feeding water from Isco syringe pump992 through the dashed line 983 b. r-Pyoil, and optionally steam, werethen fed through dashed line 981 b to the reactor. Thus, the reactor canbe operated be feeding various combinations of components and at variouslocations. Typical operating conditions were heating the first zone to600° C., the second zone to about 700° C., and the third zone to 375° C.while maintaining 3 psig at the reactor exit. Typical flow rates ofhydrocarbon feed and steam resulted in a 0.5 sec residence time in one7-inch section of the furnace. The first 7-inch section of the furnace922 a was operated as the convection zone and the second 7-inch section922 b as the radiant zone of a steam cracker. The gaseous effluent ofthe reactor exited the reactor through line 972. The stream was cooledwith shell and tube condenser 934 and any condensed liquids werecollected in glycol cooled sight glass 936. The liquid material wasremoved periodically through line 978 for weighing and gaschromatography analysis. The gas stream was fed through line 976 a forventing through a back-pressure regulator that maintained about 3 psigon the unit. The flow rate was measured with a Sensidyne GilianGilibrator-2 Calibrator. Periodically a portion of the gas stream wassent in line 976 b to a gas chromatography sampling system for analysis.The unit could be was operated in a decoking mode by physicallydisconnecting propane line 984 and attaching air cylinder 960 with line986 and flexible tubing line 974 a to mass flow controlled 994.

Analysis of reaction feed components and products was done by gaschromatography. All percentages are by weight unless specifiedotherwise. Liquid samples were analyzed on an Agilent 7890A using aRestek RTX-1 column (30 meters×320 micron ID, 0.5 micron film thickness)over a temperature range of 35° C. to 300° C. and a flame ionizationdetector. Gas samples were analyzed on an Agilent 8890 gaschromatograph. This GC was configured to analyze refinery gas up to C6with H₂S content. The system used four valves, three detectors, 2 packedcolumns, 3 micro-packed columns, and 2 capillary columns. The columnsused were the following: 2 ft× 1/16 in, 1 mm i.d. HayeSep A 80/100 meshUltiMetal Plus 41 mm; 1.7 m× 1/16 in, 1 mm i.d. HayeSep A 80/100 meshUltiMetal Plus 41 mm; 2 m× 1/16 in, 1 mm i.d. MolSieve 13×80/100 meshUltiMetal Plus 41 mm; 3 ft×⅛ in, 2.1 mm i.d. HayeSep Q 80/100 mesh inUltiMetal Plus; 8 ft×⅛ in, 2.1 mm i.d. Molecular Sieve 5 A 60/80 mesh inUltiMetal Plus; 2 m×0.32 mm, Sum thickness DB-1 (123-1015, cut); 25m×0.32 mm, 8 um thickness HP-AL/S (19091P-S12). The FID channel wasconfigured to analyze the hydrocarbons with the capillary columns fromC₁ to C₅, while C6/C6+ components are backflushed and measured as onepeak at the beginning of the analysis. The first channel (reference gasHe) was configured to analyze fixed gases (such as CO₂, CO, O2, N2, andH₂S.). This channel was run isothermally, with all micro-packed columnsinstalled inside a valve oven. The second TCD channel (third detector,reference gas N2) analyzed hydrogen through regular packed columns. Theanalyses from both chromatographs were combined based on the mass ofeach stream (gas and liquid where present) to provide an overall assayfor the reactor.

A typical run was made as follows:

Nitrogen (130 secm) was purged through the reactor system, and thereactor was heated (zone1, zone 2, zone 3 setpoints 300° C., 450° C.,300° C., respectively). Preheaters and cooler for post-reactor liquidcollection were powered on. After 15 minutes and the preheater was above100° C., 0.1 mL/min water was added to the preheater to generate steam.The reactor temperature setpoints were raised to 450° C., 600° C., and350° C. for zones 1, 2, and 3, respectively. After another 10 minutes,the reactor temperature setpoints were raised to 600° C., 700° C., and375° C. for zones 1, 2, and 3, respectively. The N₂ was decreased tozero as the propane flow was increased to 130 secm. After 100 min atthese conditions either r-pyoil or r-pyoil in naphtha was introduced,and the propane flow was reduced. The propane flow was 104 secm, and ther-pyoil feed rate was 0.051 g/hr for a run with 80% propane and 20%r-pyoil. This material was steam cracked for 4.5 hr (with gas and liquidsampling). Then, 130 sccm propane flow was reestablished. After 1 hr,the reactor was cooled and purged with nitrogen.

Steam Cracking with r-Pyoil Example 1

Table 3 contains examples of runs made in the lab steam cracker withpropane, r-pyoil from Example 1, and various weight ratios of the two.Steam was fed to the reactor in a 0.4 steam to hydrocarbon ratio in allruns. Nitrogen (5% by weight relative to the hydrocarbon) was fed withsteam in the run with only r-pyoil to aid in even steam generation.Comparative Example 1 is an example involving cracking only propane.

TABLE 3 Steam Cracking Examples using r-pyoil from Example 1. ExamplesComparative Example 1 11 12 13 14 15 Zone 2 Control Temp 700 700 700 700700 700    Propane (wt %) 100 85 80 67 50 0   r-Pyoil (wt %) 0 15 20 3350 100*    Feed Wt, g/hr 15.36 15.43 15.35 15.4 15.33 15.35 Steam/Hydrocarbon Ratio 0.4 0.4 0.4 0.4 0.4 0.4  Total Accountability, %103.7 94.9 94.5 89.8 87.7 86    Total Products Weight Percent C6+ 1.152.61 2.62 4.38 7.78 26.14  methane 18.04 18.40 17.68 17.51 17.52 12.30 ethane 2.19 2.59 2.46 2.55 2.88 2.44 ethylene 30.69 32.25 31.80 32.3632.97 23.09  propane 24.04 19.11 20.25 16.87 11.66 0.33 propylene 17.8217.40 17.63 16.80 15.36 7.34 i-butane 0.00 0.04 0.04 0.03 0.03 0.01n-butane 0.03 0.02 0.02 0.02 0.02 0.02 propydiene 0.07 0.14 0.13 0.150.17 0.14 acetylene 0.24 0.40 0.40 0.45 0.48 0.41 t-2-butene 0.00 0.190.00 0.00 0.00 0.11 1-butene 0.16 0.85 0.19 0.19 0.20 0.23 i-butylene0.92 0.34 0.87 0.81 0.66 0.81 c-2-butene 0.12 0.15 0.40 0.56 0.73 0.11i-pentane 0.13 0.00 0.00 0.00 0.00 0.00 n-pentane 0.00 0.01 0.01 0.020.02 0.02 1,3-butadiene 1.73 2.26 2.31 2.63 3.02 2.88 methyl acetylene0.20 0.26 0.26 0.30 0.32 0.28 t-2-pentene 0.11 0.08 0.12 0.12 0.12 0.052-methyl-2-butene 0.02 0.01 0.03 0.03 0.02 0.02 1-pentene 0.05 0.09 0.010.02 0.02 0.03 c-2-pentene 0.06 0.01 0.03 0.03 0.03 0.01 pentadiene 10.00 0.01 0.02 0.02 0.02 0.08 pentadiene 2 0.01 0.04 0.04 0.05 0.06 0.16pentadiene 3 0.12 0.21 0.23 0.27 0.30 0.26 1,3-Cyclopentadiene 0.48 0.850.81 1.01 1.25 1.58 pentadiene 4 0.00 0.08 0.08 0.09 0.10 0.07pentadiene 5 0.06 0.17 0.17 0.20 0.23 0.31 CO2 0.00 0.00 0.00 0.00 0.000.00 CO 0.12 0.11 0.05 0.00 0.12 0.74 hydrogen 1.40 1.31 1.27 1.21 1.130.67 Unidentified 0.00 0.00 0.10 1.33 2.79 19.37  Olefin/Aromatics Ratio45.42 21.07 20.91 12.62 7.11 1.42 Total Aromatics 1.15 2.61 2.62 4.387.78 26.14  Propylene + Ethylene 48.51 49.66 49.43 49.16 48.34 30.43 Ethylene/Propylene Ratio 1.72 1.85 1.80 1.93 2.15 3.14 *5% N2 was alsoadded to facilitate steam generation. Analysis has been normalized toexclude it.

As the amount of r-pyoil used is increased relative to propane, therewas an increase in the formation of dienes. For example, bothr-butadiene and cyclopentadiene increased as more r-pyoil is added tothe feed. Additionally, aromatics (C6+) increased considerably withincreased r-pyoil in the feed.

Accountability decreased with increasing amounts of r-pyoil in theseexamples. It was determined that some r-pyoil in the feed was being heldup in the preheater section. Due to the short run times, accountabilitywas negatively affected. A slight increase in the slope of the reactorinlet line corrected the issue (see Example 24). Nonetheless, even withan accountability of 86% in Example 15, the trend was clear. The overallyield of r-ethylene and r-propylene decreased from about 50% to lessthan about 35% as the amount of r-pyoil in the feed increased. Indeed,feeding r-pyoil alone produced about 40% of aromatics (C6+) andunidentified higher boilers (see Example 15 and Example 24).

r-Ethylene Yield—r-Ethylene yield showed an increase from 30.7% to >32%as 15% r-pyoil was co-cracked with propane. The yield of r-ethylene thenremained about 32% until >50% r-pyoil was used. With 100% r-pyoil, theyield of r-ethylene decreased to 21.5% due to a large amount ofaromatics and unidentified high boilers (>40%). Since r-pyoil cracksfaster than propane, a feed with an increased amount of r-pyoil willcrack faster to more r-propylene. The r-propylene can then react to formr-ethylene, diene and aromatics. When the concentration of r-pyoil wasincreased the amount of r-propylene cracked products was also increased.Thus, the increased amount of dienes can react with other dienes andolefins (like r-ethylene) leading to even more aromatics formation. So,at 100% r-pyoil in the feed, the amount of r-ethylene and r-propylenerecovered was lower due to the high concentration of aromatics thatformed. In fact, the olefin/aromatic dropped from 45.4 to 1.4 as r-pyoilwas increased to 100% in the feed. Thus, the yield of r-ethyleneincreased as more r-pyoil was added to the feed mixture, at least toabout 50% r-pyoil. Feeding pyoil in propane provides a way to increasethe ethylene/propylene ratio on a steam cracker.

r-Propylene Yield-r-Propylene yield decreased with more r-pyoil in thefeed. It dropped from 17.8% with propane only to 17.4% with 15% r-pyoiland then to 6.8% as 100% r-pyoil was cracked. r-Propylene formation didnot decrease in these cases. r-Pyoil cracks at lower temperature thanpropane. As r-propylene is formed earlier in the reactor it has moretime to converted to other materials-like dienes and aromatics andr-ethylene. Thus, feeding r-pyoil with propane to a cracker provides away to increase the yield of ethylene, dienes and aromatics.

The r-ethylene/r-propylene ratio increased as more r-pyoil was added tothe feed because an increase concentration of r-pyoil made r-propylenefaster, and the r-propylene reacted to other cracked products-likedienes, aromatics and r-ethylene.

The ethylene to propylene ratio increased from 1.72 to 3.14 going from100% propane to 100% r-pyoil cracking. The ratio was lower for 15%r-pyoil (0.54) than 20% r-pyoil (0.55) due to experimental error withthe small change in r-pyoil feed and the error from having just one runat each condition.

The olefin/aromatic ratio decreased from 45 with no r-pyoil in the feedto 1.4 with no propane in the feed. The decrease occurred mainly becauser-pyoil cracked more readily than propane and thus more r-propylene wasproduced faster. This gave the r-propylene more time to react further tomake more r-ethylene, dienes, and aromatics. Thus, aromatics increased,and r-propylene decreased with the olefin/aromatic ratio decreasing as aresult.

r-Butadiene increased as the concentration of r-pyoil in the feedincreased, thus providing a way to increase r-butadiene yield.r-Butadiene increased from 1.73% with propane cracking, to about 2.3%with 15-20% r-pyoil in the feed, to 2.63% with 33% r-pyoil, and to 3.02%with 50% r-pyoil. The amount was 2.88% at 100% r-pyoil. Example 24showed 3.37% r-butadiene observed in another run with 100% r-pyoil. Thisamount may be a more accurate value based on the accountability problemsthat occurred in Example 15. The increase in r-butadiene was the resultof more severity in cracking as products like r-propylene continued tocrack to other materials.

Cyclopentadiene increased with increasing r-pyoil except for thedecrease in going from 15%-20% r-pyoil (from 0.85 to 0.81). Again, someexperimental error was likely. Thus, cyclopentadiene increased from0.48% cracking propane only, to about 0.85% at 15-20% r-pyoil in thereactor feed, to 1.01% with 33% r-pyoil, to 1.25 with 50% r-pyoil, and1.58% with 100% r-pyoil. The increase in cyclopentadiene was also theresult of more severity in cracking as products like r-propylenecontinued to crack to other materials. Thus, cracking r-pyoil withpropane provided a way to increase cyclopentadiene production.

Operating with r-pyoil in the feed to the steam cracker resulted in lesspropane in the reactor effluent. In commercial operation, this wouldresult in a decreased mass flow in the recycle loop. The lower flowwould decrease cryogenic energy costs and potentially increase capacityon the plant if it is capacity constrained. Additionally, lower propanein the recycle loop would debottleneck the r-propylene fractionator ifit is already capacity limited.

Steam Cracking with r-Pyoil Examples 1-4.

Table 4 contains examples of runs made with the r-pyoil samples found inTable1 with a propane/r-pyoil weight ratio of 80/20 and 0.4 steam tohydrocarbon ratio.

TABLE 4 Examples using r-PyOil Examples 1-4 under similar conditions.Examples 16 17 18 19 r-Pyoil from Table 1 1 2 3 4 Zone 2 Control Temp700 700 700 700 Propane (wt %) 80 80 80 80 r-Pyoil (wt %) 20 20 20 20 N2(wt %) 0 0 0 0 Feed Wt, g/hr 15.35 15.35 15.35 15.35 Steam/HydrocarbonRatio 0.4 0.4 0.4 0.4 Total Accountability, % 94.5 96.4 95.6 95.3 TotalProducts Weight Percent C6+ 2.62 2.86 3.11 2.85 methane 17.68 17.3617.97 17.20 ethane 2.46 2.55 2.67 2.47 ethylene 31.80 30.83 31.58 30.64propane 20.25 21.54 19.34 21.34 propylene 17.63 17.32 17.18 17.37i-butane 0.04 0.04 0.04 0.04 n-butane 0.02 0.01 0.02 0.03 propadiene0.13 0.06 0.09 0.12 acetylene 0.40 0.11 0.26 0.37 t-2-butene 0.00 0.000.00 0.00 1-butene 0.19 0.19 0.20 0.19 i-butylene 0.87 0.91 0.91 0.98c-2-butene 0.40 0.44 0.45 0.52 i-pentane 0.00 0.14 0.16 0.16 n-pentane0.01 0.03 0.03 0.03 1,3-butadiene 2.31 2.28 2.33 2.27 methyl acetylene0.26 0.23 0.23 0.24 t-2-pentene 0.12 0.13 0.14 0.13 2-methyl-2-butene0.03 0.04 0.04 0.03 1-pentene 0.01 0.02 0.02 0.02 c-2-pentene 0.03 0.060.05 0.04 pentadiene 1 0.02 0.00 0.00 0.00 pentadiene 2 0.04 0.02 0.020.01 pentadiene 3 0.23 0.17 0.00 0.25 1,3-Cyclopentadiene 0.81 0.72 0.760.71 pentadiene 4 0.08 0.00 0.00 0.00 pentadiene 5 0.17 0.08 0.09 0.08CO2 0.00 0.00 0.00 0.00 CO 0.05 0.00 0.00 0.00 hydrogen 1.27 1.22 1.261.21 Unidentified 0.10 0.65 1.04 0.69 Olefin/Aromatics Ratio 20.91 18.6617.30 18.75 Total Aromatics 2.62 2.86 3.11 2.85 Propylene + Ethylene49.43 48.14 48.77 48.01 Ethylene/Propylene Ratio 1.80 1.78 1.84 1.76

Steam cracking of the different r-pyoil Examples 1-4 at the sameconditions gave similar results. Even the lab distilled sample ofr-pyoil (Example 19) cracked like the other samples. The highestr-ethylene and r-propylene yield was for Example 16, but the range was48.01-49.43. The r-ethylene/r-propylene ratio varied from 1.76 to 1.84.The amount of aromatics (C6+) only varied from 2.62 to 3.11. Example 16also produced the smallest yield of aromatics. The r-pyoil used for thisexample (r-Pyoil Example 1, Table 1) contained the largest amount ofparaffins and the lowest amount of aromatics. Both are desirable forcracking to r-ethylene and r-propylene.

Steam Cracking with r-Pyoil Example 2

Table 5 contains runs made in the lab steam cracker with propane(Comparative Example 2), r-pyoil Example 2, and four runs with apropane/pyrolysis oil weight ratio of 80/20. Comparative Example 2 andExample 20 were run with a 0.2 steam to hydrocarbon ratio. Steam was fedto the reactor in a 0.4 steam to hydrocarbon ratio in all otherexamples. Nitrogen (5% by weight relative to the r-pyoil) was fed withsteam in the run with only r-pyoil (Example 24).

TABLE 5 Examples using r-Pyoil Example 2. Examples Comparative Example 220 21 22 23 24 Zone 2 Control Temp 700° C. 700° C. 700° C. 700° C. 700°C 700° C. Propane (wt %) 100 80 80 80 80 0   r-Pyoil (wt %) 0 20 20 2020 100*    Feed Wt, g/hr 15.36 15.35 15.35 15.35 15.35 15.35 Steam/Hydrocarbon Ratio 0.2 0.2 0.4 0.4 0.4 0.4  Total Accountability, %100.3 93.8 99.1 93.4 96.4 97.9  Total Products Weight Percent C6+ 1.362.97 2.53 2.98 2.86 22.54  methane 18.59 19.59 17.34 16.64 17.36 11.41 ethane 2.56 3.09 2.26 2.35 2.55 3.00 ethylene 30.70 32.51 31.19 29.8930.83 24.88  propane 23.00 17.28 21.63 23.84 21.54 0.38 propylene 18.0616.78 17.72 17.24 17.32 10.94  i-butane 0.04 0.03 0.03 0.05 0.04 0.02n-butane 0.01 0.03 0.03 0.03 0.01 0.09 propadiene 0.05 0.10 0.12 0.120.06 0.12 acetylene 0.12 0.35 0.40 0.36 0.11 0.31 t-2-butene 0.00 0.000.00 0.00 0.00 0.00 1-butene 0.17 0.20 0.18 0.18 0.19 0.25 i-butylene0.87 0.80 0.91 0.94 0.91 1.22 c-2-butene 0.14 0.40 0.40 0.44 0.44 1.47i-pentane 0.14 0.13 0.00 0.00 0.14 0.13 n-pentane 0.00 0.01 0.02 0.030.03 0.01 1,3-butadiene 1.74 2.35 2.20 2.18 2.28 3.37 methyl acetylene0.18 0.22 0.26 0.24 0.23 0.23 t-2-pentene 0.13 0.14 0.12 0.12 0.13 0.142-methyl-2-butene 0.03 0.04 0.03 0.04 0.04 0.10 1-pentene 0.01 0.03 0.010.01 0.02 0.05 c-2-pentene 0.04 0.04 0.03 0.04 0.06 0.18 pentadiene 10.00 0.01 0.01 0.02 0.00 0.14 pentadiene 2 0.01 0.02 0.03 0.02 0.02 0.19pentadiene 3 0.00 0.24 0.19 0.24 0.17 0.50 1,3-Cyclopentadiene 0.52 0.830.65 0.71 0.72 1.44 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.01pentadiene 5 0.06 0.09 0.08 0.08 0.08 0.15 CO2 0.00 0.00 0.00 0.00 0.000.00 CO 0.07 0.00 0.00 0.00 0.00 0.19 hydrogen 1.36 1.28 1.28 1.21 1.220.63 Unidentified 0.00 0.00 0.34 0.00 0.65 15.89  Olefin/Aromatics Ratio38.54 18.39 21.26 17.55 18.66 2.00 Total Aromatics 1.36 2.97 2.53 2.982.86 22.54  Propylene + − Ethylene 48.76 49.29 48.91 47.13 48.14 35.82 Ethylene/Propylene Ratio 1.70 1.94 1.76 1.73 1.78 2.27 *5% N2 was alsoadded to facilitate steam generation. Analysis has been normalized toexclude it.

Comparing Example 20 to Examples 21-23 shows that the increased feedflow rate (from 192 sccm in Example 20 to 255 sccm with more steam inExamples 21-23) resulted in less conversion of propane and r-pyoil dueto the 25% shorter residence time in the reactor (r-ethylene andr-propylene: 49.3% for Example 20 vs 47.1, 48.1, 48.9% for Examples21-23). r-Ethylene was higher in Example 21 with the increased residencetime since propane and r-pyoil cracked to higher conversion ofr-ethylene and r-propylene and some of the r-propylene can then beconverted to additional r-ethylene. And conversely, r-propylene washigher in the higher flow examples with a higher steam to hydrocarbonratio (Example 21-23) since it has less time to continue reacting. Thus,Examples 21-23 produced a smaller amount of other components:r-ethylene, C6+(aromatics), r-butadiene, cyclopentadiene, etc., thanfound in Example 20.

Examples 21-23 were run at the same conditions and showed that there wassome variability in operation of the lab unit, but it was sufficientlysmall that trends can be seen when different conditions are used.

Example 24, like example 15, showed that the r-propylene and r-ethyleneyield decreased when 100% r-pyoil was cracked compared to feed with 20%r-pyoil. The amount decreased from about 48% (in Examples 21-23) to 36%.Total aromatics was greater than 20% of the product as in Example 15.

Steam Cracking with r-Pyoil Example 3

Table 6 contains runs made in the lab steam cracker with propane andr-pyoil Example 3 at different steam to hydrocarbon ratios.

TABLE 6 Examples using r-Pyoil Example 3. Examples 25 26 Zone 2 ControlTemp 700° C. 700° C. Propane (wt %) 80 80 r-Pyoil (wt %) 20 20 N2 (wt %)0 0 Feed Wt, g/hr 15.33 15.33 Steam/Hydrocarbon Ratio 0.4 0.2 TotalAccountability, % 95.6 92.1 Total Products Weight Percent C6+ 3.11 3.42methane 17.97 18.57 ethane 2.67 3.01 ethylene 31.58 31.97 propane 19.3417.43 propylene 17.18 17.17 i-butane 0.04 0.04 n-butane 0.02 0.03propadiene 0.09 0.10 acetylene 0.26 0.35 t-2-butene 0.00 0.00 1-butene0.20 0.20 i-butylene 0.91 0.88 c-2-butene 0.45 0.45 i-pentane 0.16 0.17n-pentane 0.03 0.02 1,3-butadiene 2.33 2.35 methyl acetylene 0.23 0.22t-2-pentene 0.14 0.15 2-methyl-2-butene 0.04 0.04 1-pentene 0.02 0.02c-2-pentene 0.05 0.04 pentadiene 1 0.00 0.00 pentadiene 2 0.02 0.02pentadiene 3 0.00 0.25 1,3-Cyclopentadiene 0.76 0.84 pentadiene 4 0.000.00 pentadiene 5 0.09 0.10 CO2 0.00 0.00 CO 0.00 0.00 hydrogen 1.261.24 Unidentified 1.04 0.92 Olefin/Aromatics Ratio 17.30 15.98 TotalAromatics 3.11 3.42 Propylene + Ethylene 48.77 49.14 Ethylene/PropyleneRatio 1.84 1.86

The same trends observed from cracking with r-pyoil Examples 1-2 weredemonstrated for cracking with propane and r-pyoil Example 3. Example 25compared to Example 26 showed that a decrease in the feed flow rate (to192 sccm in Example 26 with less steam from 255 sccm in Example 25)resulted in greater conversion of the propane and r-pyoil due to the 25%greater residence time in the reactor (r-ethylene and r-propylene:48.77% for Example 22 vs 49.14% for the lower flow in Example 26).r-Ethylene was higher in Example 26 with the increased residence timesince propane and r-pyoil cracked to higher conversion of r-ethylene andr-propylene and some of the r-propylene was then converted to additionalr-ethylene. Thus, Example 25, with the shorter residence time produced asmaller amount of other components: r-ethylene, C6+(aromatics),r-butadiene, cyclopentadiene, etc., than found in Example 26.

Steam Cracking with r-Pyoil Example 4

Table 7 contains runs made in the lab steam cracker with propane andpyrolysis oil sample 4 at two different steam to hydrocarbon ratios.

TABLE 7 Examples using Pyrolysis Oil Example 4. Examples 27 28 Zone 2Control Temp 700° C. 700° C. Propane (wt %) 80 80 r-Pyoil (wt %) 20 20N2 (wt %) 0 0 Feed Wt, g/hr 15.35 15.35 Steam/Hydrocarbon Ratio 0.4 0.6Total Accountability, % 95.3 95.4 Total Products Weight Percent C6+ 2.852.48 methane 17.20 15.37 ethane 2.47 2.09 ethylene 30.64 28.80 propane21.34 25.58 propylene 17.37 17.79 i-butane 0.04 0.05 n-butane 0.03 0.03propadiene 0.12 0.12 acetylene 0.37 0.35 t-2-butene 0.00 0.00 1-butene0.19 0.19 i-butylene 0.98 1.03 c-2-butene 0.52 0.53 i-pentane 0.16 0.15n-pentane 0.03 0.05 1,3-butadiene 2.27 2.15 methyl acetylene 0.24 0.25t-2-pentene 0.13 0.12 2-methyl-2-butene 0.03 0.04 1-pentene 0.02 0.02c-2-pentene 0.04 0.05 pentadiene 1 0.00 0.00 pentadiene 2 0.01 0.02pentadiene 3 0.25 0.27 1,3-Cyclopentadiene 0.71 0.65 pentadiene 4 0.000.00 pentadiene 5 0.08 0.08 CO2 0.00 0.00 CO 0.00 0.00 hydrogen 1.211.15 Unidentified 0.69 0.63 Olefin/Aromatics Ratio 18.75 20.94 TotalAromatics 2.85 2.48 Propylene + Ethylene 48.01 46.59 Ethylene/PropyleneRatio 1.76 1.62

The results in Table 7 showed the same trends as discussed with Example20 vs Examples 21-23 in Table 5 and Example 25 vs Example 26 in Table 6.At a smaller steam to hydrocarbon ratio, higher amounts of r-ethyleneand r-propylene and higher amounts of aromatics were obtained at theincreased residence time. The r-ethylene/r-propylene ratio was alsogreater.

Thus, comparing Example 20 with Examples 21-23 in Table 5, Example 25with Example 26, and Example 27 with Example 28 showed the same effect.Decreasing the steam to hydrocarbon ratio decreased the total flow inthe reactor. This increased the residence time. As a result, there wasan increase in the amount of r-ethylene and r-propylene produced. Ther-ethylene to r-propylene ratio was larger which indicated that somer-propylene reacted to other products like r-ethylene. There was also anincrease in aromatics(C6+) and dienes.

Examples of Cracking r-Pyoils from Table 2 with Propane

Table 8 contains the results of runs made in the lab steam cracker withpropane (Comparative example 3) and the six r-pyoil samples listed inTable 2. Steam was fed to the reactor in a 0.4 steam to hydrocarbonratio in all runs.

Examples 30, 33, and 34 were the results of runs with r-pyoil havinggreater than 35% C4-C7. The r-pyoil used in Example 40 contained 34.7%aromatics. Comparative Example 3 was a run with propane only. Examples29, 31, and 32 were the results of runs with r-pyoil containing lessthan 35% C4-C7.

TABLE 8 Examples of steam cracking with propane and r-pyoils. ExamplesComparative Example 3 29 30 31 32 33 34 r-Pyoil Feed from Table 2 5 6 78 9 10 Zone 2 Control Temp, ° C. 700 700 700 700 700 700 700 Propane (wt%) 100 80 80 80 80 80 80 r-Pyoil (wt %) 0 20 20 20 20 20 20 Feed Wt,g/hr 15.36 15.32 15.33 15.33 15.35 15.35 15.35 Steam/Hydrocarbon Ratio0.4 0.4 0.4 0.4 0.4 0.4 0.4 Total Accountability, % 103 100 100.3 96.796.3 95.7 97.3 Total Products Weight Percent C6+ 1.13 2.86 2.64 3.032.34 3.16 3.00 methane 17.69 17.17 15.97 17.04 16.42 18.00 16.41 ethane2.27 2.28 2.12 2.26 2.59 2.63 2.19 ethylene 29.85 31.03 29.23 30.8130.73 30.80 28.99 propane 24.90 21.86 25.13 21.70 23.79 20.99 24.57propylene 18.11 17.36 17.78 17.23 18.08 17.90 17.32 i-butane 0.05 0.040.05 0.04 0.05 0.04 0.05 n-butane 0.02 0.02 0.04 0.02 0.00 0.00 0.02propadiene 0.08 0.14 0.12 0.14 0.04 0.04 0.10 acetylene 0.31 0.42 0.360.42 0.04 0.06 0.31 t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 0.001-butene 0.16 0.18 0.19 0.18 0.19 0.20 0.18 i-butylene 0.91 0.93 1.000.92 0.93 0.90 0.95 c-2-butene 0.13 0.51 0.50 0.50 0.34 0.68 0.61i-pentane 0.14 0.00 0.15 0.00 0.16 0.16 0.15 n-pentane 0.00 0.04 0.050.04 0.00 0.00 0.06 1,3-butadiene 1.64 2.28 2.15 2.26 2.48 2.23 2.04methyl acetylene 0.19 0.28 0.24 0.28 n/a 0.24 0.24 t-2-pentene 0.12 0.120.12 0.12 0.13 0.13 0.11 2-methyl-2-butene 0.03 0.03 0.03 0.03 0.04 0.030.03 1-pentene 0.11 0.02 0.02 0.02 0.01 0.02 0.02 c-2-pentene 0.01 0.030.04 0.03 0.11 0.10 0.05 pentadiene 1 0.00 0.02 0.00 0.02 0.00 0.00 0.00pentadiene 2 0.01 0.03 0.03 0.04 0.01 0.05 0.02 pentadiene 3 0.14 0.250.00 0.25 0.00 0.00 0.00 1,3-Cyclopentadiene 0.44 0.77 0.69 0.77 0.220.30 0.63 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 50.06 0.08 0.08 0.08 0.09 0.08 0.07 CO2 0.00 0.00 0.00 0.00 0.00 0.000.00 CO 0.11 0.00 0.07 0.00 0.00 0.00 0.11 hydrogen 1.36 1.26 1.21 1.251.18 1.25 1.22 unidentified 0.00 0.00 0.00 0.52 0.00 0.00 0.56Olefin/Aromatics Ratio 45.81 18.79 19.66 17.64 22.84 16.91 17.06 TotalAromatics 1.13 2.86 2.64 3.03 2.34 3.16 3.00 Propylene + Ethylene 47.9648.39 47.01 48.04 48.82 48.70 46.31 Ethylene/Propylene Ratio 1.65 1.791.64 1.79 1.70 1.72 1.67

The examples in Table 8 involved using an 80/20 mix of propane with thevarious distilled r-pyoils. The results were like those in previousexamples involving cracking r-pyoil with propane. All the examplesproduced an increase in aromatics and dienes relative to crackingpropane only. As a result, the olefins to aromatic ratio was lower forcracking the combined feeds. The amount of r-propylene and r-ethyleneproduced was 47.01-48.82% for all examples except for the 46.31%obtained with the r-pyoil with 34.7% aromatic content (using r-pyoilExample 10 in Example 34). Except for that difference, the r-pyoilsperformed similarly, and any of them can be fed with C-2 to C-4 in asteam cracker. r-Pyoils having high aromatic content like r-pyoilExample 10 may not be the preferred feed for a steam cracker, and ar-pyoil having less than about 20% aromatic content should be considereda more preferred feed for co-cracking with ethane or propane.

Example of Steam Cracking r-Pyoils from Table 2 with Natural Gasoline

Table 9 contains the results of runs made in the lab steam cracker witha natural gasoline sample from a supplier and the r-pyoils listed inTable 2. The natural gasoline material was greater than 99% C5-C8 andcontained greater than 70% identified paraffins and about 6% aromatics.The material had an initial boiling point of 100° F., a 50% boilingpoint of 128° F., a 95% boiling point of 208° F., and a final boilingpoint of 240° F. No component greater than C9 were identified in thenatural gasoline sample. It was used as a typical naphtha stream for theexamples.

The results presented in Table 9 include examples involving cracking thenatural gasoline (Comparative example 4), or cracking a mixture ofnatural gasoline and the r-pyoil samples listed in Table 2. Steam wasfed to the reactor in a 0.4 steam to hydrocarbon ratio in all runs.Nitrogen (5% by weight relative to the hydrocarbon) was fed with waterto facilitate even steam generation. Examples 35, 37, and 38 involvedruns with r-pyoils containing very little C15+. Example 38 illustratedthe results of a run with greater than 50% C15+ in the r-pyoil.

The gas flow of the reactor effluent and the gas chromatography analysisof the stream were used to determine the weight of gas product, and thenthe weight of other liquid material needed for 100% accountability wascalculated. This liquid material was typically 50-75% aromatics, andmore typically 60-70%. An actual assay of the liquid sample wasdifficult for these examples. The liquid product in most of theseexamples was an emulsion that was hard to separate and assay. Since thegas analysis was reliable, this method allowed an accurate comparison ofthe gaseous products while still having an estimate of the liquidproduct if it was completely recovered.

TABLE 9 Results of Cracking r-Pyoil with Natural Gasoline. ExamplesComparative Example 4 35 36 37 38 39 40 r-Pyoil Feed Natural 5   6   7  8   9   10    from Table 2 Gasoline Zone 2 Control Temp 700    700   700    700    700    700    700    Natural Gasoline (wt %) 100    80   80    80    80    80    80    r-Pyoil (wt %) 0   20    20    20    20   20    20    N2 (wt %) 5*   5*   5*   5*   5*   5*   5*   Feed Wt, g/hr15.4  15.3  15.4  15.4  15.4  15.4  15.4  Gas Exit Flow, sccm 221.2  206.7   204.5   211.8   211.3   202.6   207.8   Gas Weight 92.5  83.1 81.5  79.9  83.9  81.7  84.3  Accountability, % Total Products WeightPercent C6+ 9.54 7.86 6.32 8.05 7.23 7.15 5.75 methane 19.19  18.33 16.98  17.80  19.46  17.88  15.67  ethane 3.91 3.91 3.24 3.86 4.02 3.522.77 ethylene 27.34  26.14  28.24  24.96  27.74  26.42  29.39  propane0.42 0.40 0.38 0.36 0.37 0.37 0.42 propylene 12.97  12.49  13.61  10.87 11.80  12.34  16.10  i-butane 0.03 0.03 0.03 0.02 0.02 0.02 0.03n-butane 0.11 0.07 0.00 0.05 0.00 0.05 0.00 propadiene 0.22 0.18 0.100.18 0.08 0.22 0.11 acetylene 0.40 0.34 0.11 0.33 0.09 0.41 0.13t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.44 0.39 0.400.32 0.38 0.39 0.46 i-butylene 0.91 0.89 0.91 0.65 0.76 0.86 1.30c-2-butene 2.98 2.85 2.98 2.28 2.58 2.94 3.58 i-pentane 0.08 0.03 0.020.05 0.04 0.03 0.02 n-pentane 5.55 1.95 0.84 2.21 1.72 1.45 1.331,3-butadiene 3.17 3.09 3.77 2.94 3.54 3.48 3.78 methyl acetylene 0.370.32 0.40 0.31 0.36 0.39 n/a t-2-pentene 0.14 0.12 0.12 0.12 0.14 0.120.12 2-methyl-2-butene 0.07 0.06 0.04 0.07 0.08 0.07 0.06 1-pentene 0.100.08 0.08 0.09 0.11 0.10 0.09 c-2-pentene 0.20 0.17 0.07 0.19 0.12 0.090.08 pentadiene 1 0.35 0.12 0.02 0.19 0.13 0.09 0.06 pentadiene 2 0.800.52 0.16 0.59 0.54 0.40 0.29 pentadiene 3 0.48 0.10 0.00 0.46 0.00 0.000.00 1,3-Cyclopentadiene 1.03 1.00 0.56 0.98 0.56 1.09 0.56 pentadiene 40.00 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 5 0.11 0.11 0.13 0.10 0.130.12 0.00 CO2 0.01 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.00 0.00 0.10 0.000.00 0.06 0.13 hydrogen 1.00 0.92 0.94 0.87 0.95 0.93 1.03 Other High8.09 17.54  19.45  21.12  17.06  19.01  16.75  Boilers-calculated** C6+and Other 17.63  25.40  25.77  29.17  24.28  26.17  22.50  CalculatedHigh Boilers Ethylene and Propylene 40.31  38.63  41.86  35.83  39.54 38.76  45.48  Ethylene/Propylene Ratio 2.11 2.09 2.07 2.30 2.35 2.141.83 Olefin/Aromatics 5.38 6.15 8.10 5.59 6.74 6.81 9.74 in gas effluent*5% Nitrogen was also added to facilitate steam generation. Analysis hasbeen normalized to exclude it. **Calculated theoretical amount neededfor 100% accountability based on the actual reactor effluent gas flowrate and gas chromatography analysis.

The cracking examples in Table 9 involved using an 80/20 mix of naturalgasoline with the various distilled r-pyoils. The natural gasoline andr-pyoils examples produced an increase in C6+(aromatics), unidentifiedhigh boilers, and dienes relative to cracking propane only or r-pyoiland propane (see Table 8). The increase in aromatics in the gas phasewas about double compared to cracking 20% by weight r-pyoil withpropane. Since the liquid product was typically greater than 60%aromatics, the total amount of aromatics was probably 5 times greaterthan cracking 20% by weight r-pyoil with propane. The amount ofr-propylene and r-ethylene produced was generally lower by about 10%.The r-ethylene and r-propylene yield ranged from 35.83-41.86% for allexamples except for the 45.48% obtained with high aromatic r-pyoil(using Example 10 material in Example 40). This is almost in the rangeof the yields obtained from cracking r-pyoil and propane (46.3-48.8% inTable 7). Example 40 produced the highest amount of r-propylene (16.1%)and the highest amount of r-ethylene (29.39%). This material alsoproduced the lowest r-ethylene/r-propylene ratio which suggests thatthere was less conversion of r-propylene to other products than in theother examples. This result was unanticipated. The high concentration ofaromatics (34.7%) in the r-pyoil feed appeared to inhibit furtherreaction of r-propylene. It is thought that r-pyoils having an aromaticcontent of 25-50% will see similar results. Co-cracking this materialwith natural gasoline also produced the lowest amount of C6+ andunidentified high boilers, but this stream produced the mostr-butadiene. The natural gasoline and r-pyoil both cracked easier thanpropane so the r-propylene that formed reacted to give the increase inr-ethylene, aromatics, dienes, and others. Thus, ther-ethylene/r-propylene ratio was above 2 in all these examples, exceptin Example 40. The ratio in this example (1.83) was similar to the1.65-1.79 range observed in Table 8 for cracking r-pyoil and propane.Except for these differences, the r-pyoils performed similarly and anyof them can be fed with naphtha in a steam cracker.

Steam Cracking r-Pyoil with Ethane

Table 10 shows the results of cracking ethane and propane alone, andcracking with r-pyoil Example 2. The examples from cracking eitherethane or ethane and r-pyoil were operated at three Zone 2 controltemperatures: 700° C., 705° C., and 710° C.

TABLE 10 Examples of Cracking Ethane and r-pyoil at differenttemperatures. Examples Comparative Comparative Comparative ComparativeComparative Example 5 41 Example 6 42 Example 7 43 Example 3 Example 8Zone 2 Control Temp 700° C. 700° C. 705° C. 705° C. 710° C. 710° C. 700°C. 700° C. Propane or Ethane in Feed Ethane Ethane Ethane Ethane EthaneEthane Propane Propane Propane or Ethane (wt %) 100 80 100 80 100 80 10080 r-Pyoil (wt %) 0 20 0 20 0 20 0 20 Feed Wt, g/hr 10.48 10.47 10.4810.47 10.48 10.47 15.36 15.35 Steam/Hydrocarbon Ratio 0.4 0.4 0.4 0.40.4 0.4 0.4 0.4 Total Accountability, % 107.4 94.9 110.45 97.0 104.496.8 103.0 96.4 Total Products Weight Percent C6+ 0.22 1.42 0.43 2.180.64 2.79 1.13 2.86 methane 1.90 6.41 2.67 8.04 3.69 8.80 17.69 17.36ethane 46.36 39.94 38.75 33.77 32.15 26.82 2.27 2.55 ethylene 44.8944.89 51.27 48.53 55.63 53.41 29.85 30.83 propane 0.08 0.18 0.09 0.180.10 0.16 24.90 21.54 propylene 0.66 2.18 0.84 1.99 1.03 1.86 18.1117.32 i-butane 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.04 n-butane 0.000.00 0.00 0.00 0.00 0.00 0.02 0.01 propadiene 0.41 0.26 0.37 0.22 0.310.19 0.08 0.06 acetylene 0.00 0.01 0.00 0.01 0.00 0.01 0.31 0.11t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.04 0.070.05 0.07 0.06 0.07 0.16 0.19 i-butylene 0.00 0.15 0.00 0.15 0.00 0.140.91 0.91 c-2-butene 0.12 0.19 0.13 0.11 0.13 0.08 0.13 0.44 i-pentane0.59 0.05 0.04 0.06 0.05 0.06 0.14 0.14 n-pentane 0.01 0.01 0.00 0.000.00 0.00 0.00 0.03 1,3-butadiene 0.96 1.45 1.34 1.69 1.72 2.06 1.642.28 methyl acetylene n/a n/a n/a n/a n/a n/a 0.19 0.23 t-2-pentene 0.030.04 0.02 0.04 0.03 0.05 0.12 0.13 2-methyl-2-butene 0.02 0.00 0.03 0.000.03 0.00 0.03 0.04 1-pentene 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.02c-2-pentene 0.03 0.04 0.03 0.04 0.03 0.03 0.01 0.06 pentadiene 1 0.000.00 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 2 0.00 0.00 0.00 0.00 0.000.00 0.01 0.02 pentadiene 3 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.171,3-Cyclopentadiene 0.03 0.06 0.02 0.05 0.02 0.05 0.44 0.72 pentadiene 40.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 5 0.00 0.03 0.00 0.030.00 0.03 0.06 0.08 CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.000.00 0.00 0.00 0.00 0.00 0.11 0.00 hydrogen 3.46 2.66 3.94 2.90 4.363.43 1.36 1.22 unidentified 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.65Olefin/Aromatics 216.63 34.87 126.61 24.25 91.78 20.80 45.81 18.66 TotalAromatics 0.22 1.42 0.43 2.18 0.64 2.79 1.13 2.86 Propylene + Ethylene45.56 47.07 52.11 50.52 56.65 55.28 47.96 48.14 Ethylene/Propylene Ratio67.53 20.59 60.95 24.44 54.13 28.66 1.65 1.78

A limited number of runs with ethane were made. As can be seen in theComparative Examples 5-7 and Comparative Example 3, conversion of ethaneto products occurred more slowly than with propane. Comparative Example5 with ethane and Comparative Example 3 with propane were run at thesame molar flow rates and temperatures. However, conversion of ethanewas only 52% (100%-46% ethane in product) vs 75% for propane. However,the r-ethylene/r-propylene ratio was much higher (67.53 vs 1.65) asethane cracking produced mainly r-ethylene. The olefin to aromaticsratio for ethane cracking was also much higher for ethane cracking. TheComparative Examples 5-7 and Examples 41-43 compare cracking ethane toan 80/20 mixture of ethane and r-pyoil at 700° C., 705° C. and 710° C.Production of total r-ethylene plus r-propylene increased with bothethane feed and the combined feed when the temperature was increased (anincrease from about 46% to about 55% for both). Although the r-ethyleneto r-propylene ratio decreased for ethane cracking with increasingtemperature (from 67.53 at 700° C. to 60.95 at 705° C. to 54.13 at 710°C.), the ratio increased for the mixed feed (from 20.59 to 24.44 to28.66). r-Propylene was produced from the r-pyoil and some continued tocrack generating more cracked products such as r-ethylene, dienes andaromatics. The amount of aromatics in propane cracking with r-pyoil at700° C. (2.86% in Comparative Example 8) was about the same as crackingethane and r-pyoil at 710° C. (2.79% in Example 43).

Co-cracking ethane and r-pyoil required higher temperature to obtainmore conversion to products compared to co-cracking with propane andr-pyoil. Ethane cracking produced mainly r-ethylene. Since a hightemperature was required to crack ethane, cracking a mixture of ethaneand r-pyoil produced more aromatics and dienes as some r-propylenereacted further. Operation in this mode would be appropriate ifaromatics and dienes were desired with minimal production ofr-propylene.

Examples of Cracking r-Pyoil and Propane 5° C. Higher or Lower thanCracking Propane

Table 11 contains runs made in the lab steam cracker with propane at695° C., 700° C., and 705° C. (Comparative examples 3, 9-10) andExamples 44-46 using 80/20 propane/r-pyoil weight ratios at thesetemperatures. Steam was fed to the reactor in a 0.4 steam to hydrocarbonratio in all runs. r-Pyoil Example 2 was cracked with propane in theseexamples.

TABLE 11 Examples using r-Pyoil Example 2 at 700° C. +/− 5° C. ExamplesComparative Comparative Comparative Example 9 Example 3 Example 10 44 4546 Zone 2 Control Temp, ° C. 695 700 705 695 700 705 Propane (wt %) 100100 100 80 80 80 r-Pyoil Example 2 (wt %) 0 0 0 20 20 20 Zone 2 ExitTemp, ° C. 683 689 695 685 691 696 Feed Wt, g/hr 15.36 15.36 15.36 15.3515.35 15.35 Steam/Hydrocarbon 0.4 0.4 0.4 0.4 0.4 0.4 Ratio TotalAccountability, % 105 103 100.2 99.9 96.4 94.5 Total Products WeightPercent C6+ 0.76 1.13 1.58 2.44 2.86 4.02 methane 15.06 17.69 20.0214.80 17.36 19.33 ethane 1.92 2.27 2.49 2.20 2.55 2.63 ethylene 25.7629.85 33.22 27.14 30.83 33.06 propane 33.15 24.90 18.96 28.21 21.5415.38 propylene 18.35 18.11 16.61 17.91 17.32 15.43 i-butane 0.05 0.050.03 0.06 0.04 0.03 n-butane 0.02 0.02 0.02 0.03 0.01 0.02 propadiene0.07 0.08 0.10 0.10 0.06 0.12 acetylene 0.22 0.31 0.42 0.27 0.11 0.47t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.15 0.16 0.16 0.190.19 0.17 i-butylene 0.95 0.91 0.80 1.01 0.91 0.72 c-2-butene 0.11 0.130.13 0.49 0.44 0.33 i-pentane 0.12 0.14 0.13 0.15 0.14 0.12 n-pentane0.00 0.00 0.00 0.02 0.03 0.02 1,3-butadiene 1.22 1.64 2.00 1.93 2.282.39 methyl acetylene 0.14 0.19 0.23 0.20 0.23 0.26 t-2-pentene 0.110.12 0.12 0.12 0.13 0.12 2-methyl-2-butene 0.02 0.03 0.02 0.04 0.04 0.031-pentene 0.11 0.11 0.05 0.02 0.02 0.01 c-2-pentene 0.01 0.01 0.06 0.040.06 0.03 pentadiene 1 0.00 0.00 0.00 0.01 0.00 0.00 pentadiene 2 0.000.01 0.01 0.01 0.02 0.01 pentadiene 3 0.12 0.14 0.16 0.24 0.17 0.221,3-Cyclopentadiene 0.30 0.44 0.59 0.59 0.72 0.83 pentadiene 4 0.00 0.000.00 0.00 0.00 0.00 pentadiene 5 0.05 0.06 0.06 0.07 0.08 0.08 CO2 0.000.00 0.00 0.00 0.00 0.00 CO 0.00 0.11 0.47 0.00 0.00 0.00 hydrogen 1.211.36 1.50 1.09 1.22 1.32 unidentified 0.00 0.00 0.00 0.61 0.65 2.84Olefin/Aromatics Ratio 62.38 45.81 34.23 20.43 18.66 13.33 TotalAromatics 0.76 1.13 1.58 2.44 2.86 4.02 Propylene + Ethylene 44.12 47.9649.83 45.05 48.14 48.49 Ethylene/Propylene Ratio 1.40 1.65 2.00 1.521.78 2.14

Operating at a higher temperature in the propane tube gave a higherconversion of propane—mainly to r-ethylene and r-propylene (increasingfrom 44.12% to 47.96% to 49.83% in Comparative Example 9, 3, and 10respectively). The higher the temperature the more r-ethylene wasproduced at the expense of r-propylene (r-ethylene/r-propylene ratioincreased from 1.40 to 1.65 to 2.0 in Comparative Examples 9, 3, and10). Aromatics also increased with higher temperature. The same trendswere observed with cracking the mixed streams in Examples 44-46:increased r-ethylene and r-propylene from 45.05% to 48.49%), increasedr-ethylene/r-propylene ratio (from 1.52 to 2.14), and an increase intotal aromatics (from 2.44% to 4.02%). It is known that r-pyoilconversion to cracked products is greater at a given temperaturerelative to propane.

For the condition where the mixed feed has a 5° C. lower reactor outlettemperature consider the following two cases:

-   -   Case A. Comparative Example 3 (Propane at 700° C.) and Example        441 (80/20 at 695° C.)    -   Case B. Comparative Example 103 (Propane at 705° C.) and Example        452 (80/20 at 700° C.)

Operating the combined tube at 5° C. lower temperature allowed isolationof more r-propylene relative to the higher temperature. For example,operating at 700° C. in Example 45 vs 705° C. in Example 46, r-propylenewas 17.32% vs 15.43%. Similarly, operating at 695° C. in Example 44 vs700° C. in Example 45, r-propylene was 17.91% vs 17.32%. r-Propylene andr-ethylene yield increased as temperature was increased, but thisoccurred at the expense of r-propylene as shown by the increasingr-ethylene to r-propylene ratio (from 1.52 at 695° C. in Example 44 to2.14 at 705° C. in Example 46). The ratio also increased for propanefeed, but it started from a slightly lower level. Here, the ratioincreased from 1.40 at 695° C. to 2.0 at 705° C.

The lower temperature in the combined tube still gave almost as goodconversion to r-ethylene and r-propylene (For Case A: 47.96% for propanecracking vs 45.05% for combined cracking and for Case B: 49.83% forpropane cracking vs 48.15% combined). Operation of the combined tube atlower temperature also decreased aromatics and dienes. Thus, this modeis preferred if more r-propylene is desired relative to r-ethylene whileminimizing production of C6+(aromatics) and dienes.

For the condition where the mixed tube has a 5° C. higher reactor outlettemperature, consider the following two cases:

-   -   Case A. Comparative Example 3 (Propane at 700° C. and Example 46        (80/20 at 705° C.)    -   Case B. Comparative Example 9 (Propane at 695° C.) and Example        45 (80/20 at 700° C.)

Running lower temperature in the propane tube decreased the conversionof propane and decreased the r-ethylene to r-propylene ratio. The ratiowas lower at lower temperatures for both the combined feed and thepropane feed cases. The r-pyoil conversion to cracked products wasgreater at a given temperature relative to propane. It was seen thatoperating 5° C. higher in the combined tube caused production of morer-ethylene and less r-propylene relative to the lower temperature. Thismode—with the higher temperature in the combined tube-gave an increasedconversion to r-ethylene plus r-propylene (For Case A: 47.96% forpropane cracking in Comparative Example 3 vs 48.49% in Example 46 forcombined cracking, and for Case B: 44.11% for propane cracking(Comparative Example 9) vs 48.15% for combined cracking (Example 45) at5° C. higher temperature).

Operation in this mode (5° C. higher temperature in the combined tube)increases production of r-ethylene, aromatics, and dienes, if sodesired. By operating the propane tube at a lower temperature—whichoperates at a lower ethylene to propylene ratio—the r-propyleneproduction can be maintained compared to running both tubes at the sametemperature. For example, operating the combined tube at 700° C. and thepropane tube at 695° C. resulted in 18.35% and 17.32%, respectively, ofr-propylene. Running both at 695° C. would give 0.6% more r-propylene inthe combined tube. Thus, this mode is preferred if more aromatics,dienes, and slightly more r-ethylene is desired while minimizingproduction loss of r-propylene.

The temperatures were measured at the exit of Zone 2 which is operatedto simulate the radiant zone of the cracking furnace. These temperaturesare shown in Table 11. Although there were considerable heat loses inoperating a small lab unit, the temperatures showed that the exittemperatures for the combined feed cases were 1-2° C. higher than forthe corresponding propane only feed case. Steam cracking is anendothermic process. There is less heat needed in cracking with pyoiland propane than when cracking propane alone, and thus the temperaturedoes not decrease as much.

Examples Feeding r-Pyoil or r-Pyoil and Steam at Various Locations

Table 12 contains runs made in the lab steam cracker with propane andr-pyoil Example 3. Steam was fed to the reactor in a 0.4 steam tohydrocarbon ratio in all runs. r-Pyoil and steam were fed at differentlocations (see configurations in FIG. 11). In Example 48, the reactorinlet temperature was controlled at 380° C., and r-pyoil was fed as agas. The reactor inlet temperature was usually controlled at 130-150° C.when r-pyoil was fed as a liquid (Example 49) in the typical reactorconfiguration.

TABLE 12 Examples with r-Pyoil and Steam Fed at Different Locations.Examples* 47 48 49 50 51 52 Zone 2 Control Temp 700° C. 700° C. 700° C.700° C. 700° C. 700° C. Propane (wt %) 80 80 80 80 80 80 r-Pyoil (wt %)20 20 20 20 20 20 Feed Wt, g/hr 15.33 15.33 15.33 15.33 15.33 15.33Steam/hydrocarbon ratio 0.4 0.4 0.4 0.4 0.4 0.4 Total Accountability, %95.8 97.1 97.83 97.33 96.5 97.3 Total Products Weight Percent C6+ 3.033.66 4.50 3.32 3.03 3.38 methane 17.37 18.49 19.33 17.46 19.85 17.38ethane 2.58 3.04 3.27 2.60 3.18 2.35 ethylene 30.30 31.07 31.53 30.9332.10 30.75 propane 21.90 19.10 16.57 20.11 17.79 21.96 propylene 16.8216.78 15.97 17.24 16.64 16.14 i-butane 0.04 0.04 0.03 0.04 0.03 0.04n-butane 0.04 0.03 0.03 0.03 0.03 0.03 propadiene 0.10 0.09 0.09 0.110.11 0.12 acetylene 0.35 0.33 0.33 0.36 0.34 0.40 t-2-butene 0.00 0.000.00 0.00 0.00 0.00 1-butene 0.19 0.19 0.19 0.19 0.18 0.18 i-butylene0.94 0.79 0.72 0.86 0.73 0.86 c-2-butene 0.43 0.39 0.39 0.43 0.37 0.39i-pentane 0.16 0.16 0.16 0.16 0.15 0.15 n-pentane 0.04 0.02 0.02 0.030.02 0.04 1,3-butadiene 2.15 2.16 2.22 2.28 2.20 2.29 methyl acetylene0.21 0.21 0.20 0.23 0.22 0.24 t-2-pentene 0.13 0.13 0.13 0.13 0.12 0.122-methyl-2-butene 0.04 0.03 0.03 0.03 0.03 0.03 1-pentene 0.02 0.01 0.020.02 0.02 0.02 c-2-pentene 0.05 0.03 0.03 0.03 0.03 0.04 pentadiene 10.00 0.00 0.01 0.00 0.00 0.00 pentadiene 2 0.03 0.02 0.02 0.02 0.01 0.01pentadiene 3 0.25 0.07 0.22 0.24 0.22 0.24 1,3-Cyclopentadiene 0.72 0.760.83 0.80 0.79 0.81 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00pentadiene 5 0.08 0.08 0.08 0.08 0.08 0.08 CO2 0.00 0.00 0.00 0.00 0.050.00 CO 0.00 0.00 0.00 0.00 0.23 0.00 hydrogen 1.24 1.23 1.23 1.21 1.421.25 Unidentified 0.79 1.09 1.80 1.06 0.00 0.71 Olefin/Aromatics Ratio17.27 14.36 11.67 16.08 17.71 15.43 Total Aromatics 3.03 3.66 4.50 3.323.03 3.38 Propylene + Ethylene 47.12 47.85 47.50 48.17 48.75 46.89Ethylene/Propylene Ratio 1.80 1.85 1.97 1.79 1.93 1.91 *Example 47-r-Pyoil fed between zone 1 and zone 2: Proxy For Crossover *Example 48-r-Pyoil and steam fed between zone 1 and zone 2: Proxy for Crossover*Example 49- r-Pyoil and steam fed at midpoint of zone 1: Proxy forDownstream of Inlet *Example 50- r-Pyoil fed at midpoint of zone 1:Proxy for Downstream of Inlet *Example 51- r-Pyoil fed as gas at inletof zone 1 *Example 49- r-Pyoil fed as liquid at inlet of zone 1

Feeding propane and r-pyoil as a gas at reactor inlet (Example 51) gavea higher conversion to r-ethylene and r-propylene compared to Example 52where the r-pyoil was fed as a liquid. Some conversion was due toheating the stream to near 400° C. where some cracking occurred. Sincethe r-pyoil was vaporized outside the reactor, no heat supplied for thatpurpose was required by the furnace. Thus, more heat was available forcracking. As a result, a greater amount of r-ethylene and r-propylene(48.75%) was obtained compared to that obtained when the r-pyoil was fedas a liquid at the top of the reactor (46.89% in Example 52).Additionally, r-pyoil entering the reactor as a gas decreased residencetime in the reactor which resulted in lower total aromatics and anincreased olefin/aromatics ratio for Example 51.

In the other examples (47-50) either r-pyoil or r-pyoil and steam wasfed at the simulated crossover between the convection zone and theradiant zone of a steam cracking furnace (between Zone 1 and Zone 2 ofthe lab furnace) or at the mid-point of Zone 1. There was littledifference in the cracking results except for the aromatic content inExample 49. Feeding r-pyoil and steam at the midpoint of Zone 1 resultedin the greatest amount of aromatics. The number of aromatics was alsohigh when steam was cofed with r-pyoil between Zone 1 and Zone 2(Example 48). Both examples had a longer overall residence time forpropane to react before the streams were combined compared to the otherExamples in the table. Thus, the particular combination of longerresidence time for cracking propane and a slightly shorter residencetime for r-pyoil cracking in Example 49 resulted in a greater amount ofaromatics as cracked products.

Feeding r-pyoil as a liquid at the top of reactor (Example 52) gave thelowest conversion of all the conditions. This was due to the r-pyoilrequiring vaporization which needed heat. The lower temperature in Zone1 resulted in less cracking when compared to Example 51.

Higher conversion to r-ethylene and r-propylene was obtained by feedingthe r-pyoil at the crossover or the midpoint of the convection sectionfor one main reason. The propane residence time in the top of thebed-before introduction of r-pyoil or r-pyoil and steam—was lower. Thus,propane can achieve higher conversion to r-ethylene and r-propylenerelative to Example 52 with a 0.5 sec residence time for the entire feedstream. Feeding propane and r-pyoil as a gas at reactor inlet (Example51) gave the highest conversion to r-ethylene and r-propylene becausenone of the furnace heat was used in vaporization of r-pyoil as wasrequired for the other examples.

Decoking Examples from Cracking r-Pyoil Example 5 with Propane orNatural Gasoline

Propane was cracked at the same temperature and feed rate as an 80/20mixture of propane and r-pyoil from Example 5 and an 80/20 mixture ofnatural gasoline and r-pyoil from Example 5. All examples were operatedin the same way. The examples were run with a Zone 2 control temperatureof 700° C. When the reactor was at stable temperature, propane wascracked for 100 minutes, followed by 4.5 hr of cracking propane, orpropane and r-pyoil, or natural gasoline and r-pyoil, followed byanother 60 min of propane cracking. The steam/hydrocarbon ratio wasvaried in these comparative examples from 0.1 to 0.4. The propanecracking results are shown in Table 13 as Comparative Examples 11-13.The results presented in Table 14 include examples (Examples 53-58)involving cracking an 80/20 mixture of propane or natural gasoline withr-pyoil from Example 5 at different steam to hydrocarbon ratios.Nitrogen (5% by weight relative to the hydrocarbon) was fed with steamin the examples with natural gasoline and r-pyoil to provide even steamgeneration. In the examples involving cracking r-pyoil with naturalgasoline, the liquid samples were not analyzed. Rather, the measuredreactor effluent gas flow rate and gas chromatography analysis were usedto calculate the theoretical weight of unidentified material for 100%accountability.

Following each steam cracking run, decoking of the reactor tube wasperformed. Decoking involved heating all three zones of the furnace to700° C. under 200 sccm N2 flow and 124 sccm steam. Then, 110 sccm airwas introduced to bring the oxygen concentration to 5%. Then, the airflow was slowly increased to 310 sccm as the nitrogen flow was decreasedover two hours. Next, the furnace temperature was increased to 825° C.over two hours. These conditions were maintained for 5 hours. Gaschromatography analysis were performed every 15 minutes beginning withthe introduction of the air stream. The amount of carbon was calculatedbased on the amount of CO2 and CO in each analysis. The amount of carbonwas totalized until no CO was observed, and the amount of CO2 was lessthan 0.05%. The results (mg carbon by gas chromatography analysis) fromdecoking the propane comparative examples are found in Table 13. Theresults from the r-pyoil examples is found in Table 14.

TABLE 13 Comparative Examples of Cracking with Propane. ExamplesComparative Comparative Comparative Example 11 Example 12 Example 13Zone 2 Control Temp, ° C. 700° C. 700° C. 700° C. Propane (wt %) 100 100100 r-Pyoil (wt %) 0 0 0 N2 (wt %) 0 0 0 Feed Wt, g/hr 15.36 15.36 15.36Steam/Hydrocarbon Ratio 0.1 0.2 0.4 Total Accountability, % 98.71 101.3099.96 Total Products Weight Percent C6+ 1.71 1.44 1.10 Methane 20.3419.92 17.98 Ethane 3.04 2.83 2.25 Ethylene 32.48 32.29 30.43 Propane19.04 20.26 24.89 Propylene 17.72 17.88 18.19 i-butane 0.04 0.04 0.04n-butane 0.03 0.00 0.00 Propadiene 0.08 0.04 0.04 Acetylene 0.31 0.030.04 t-2-butene 0.00 0.00 0.00 1-butene 0.18 0.18 0.17 i-butylene 0.780.82 0.93 c-2-butene 0.15 0.14 0.13 i-pentane 0.15 0.15 0.14 n-pentane0.00 0.00 0.00 1,3-butadiene 1.93 1.90 1.68 methyl acetylene 0.18 0.180.19 t-2-pentene 0.14 0.14 0.12 2-methyl-2-butene 0.03 0.03 0.031-pentene 0.01 0.01 0.01 c-2-pentene 0.01 0.11 0.10 pentadiene 1 0.000.00 0.00 pentadiene 2 0.01 0.01 0.01 pentadiene 3 0.00 0.00 0.001,3-Cyclopentadiene 0.17 0.16 0.14 pentadiene 4 0.00 0.00 0.00pentadiene 5 0.07 0.00 0.01 CO2 0.00 0.00 0.00 CO 0.00 0.00 0.00Hydrogen 1.41 1.43 1.39 Unidentified 0.00 0.00 0.00 Olefin/AromaticsRatio 31.53 37.20 47.31 Total Aromatics 1.71 1.44 1.10 Propylene +Ethylene 50.20 50.17 48.62 Ethylene/Propylene Ratio 1.83 1.81 1.67Carbon from Decoking, mg 16 51 1.5

TABLE 14 Examples of Cracking Propane or Natural Gasoline and r-Pyoil.Examples 53 54 55 56 57 58 Propane or Natural Gasoline Propane PropanePropane Nat Gas Nat Gas Nat Gas Zone 2 Control Temp 700    700    700   700    700    700    Propane/Nat Gas (wt %) 80    80    80    80   80    80    r-Pyoil (wt %) 20    20    20    20    20    20    N2 (wt %)0   0   0   5*   5*   5*   Feed Wt, g/hr 15.32  15.32  15.32  15.29 15.29  15.29  Steam/Hydrocarbon Ratio 0.1  0.2  0.4  0.4  0.6  0.7 Total Accountability, % 95.4  99.4  97.5  100**   100**   100**   TotalProducts Weight Percent C6+ 2.88 2.13 2.30 5.69 4.97 5.62 Methane 18.83 16.08  16.62  15.60  16.81  18.43  Ethane 3.56 2.85 2.27 2.97 3.43 3.63Ethylene 30.38  28.17  30.20  27.71  27.74  26.94  Propane 19.81  25.60 24.07  0.40 0.43 0.36 Propylene 18.37  18.83  18.13  14.76  14.48 12.04  i-butane 0.04 0.06 0.05 0.03 0.03 0.02 n-butane 0.00 0.00 0.000.00 0.00 0.00 Propadiene 0.05 0.05 0.04 0.09 0.09 0.08 Acetylene 0.040.04 0.05 0.12 0.10 0.10 t-2-butene 0.00 0.00 0.00 0.00 0.00 0.001-butene 0.23 0.22 0.19 0.45 0.43 0.44 i-butylene 0.81 0.97 0.97 1.271.02 1.04 c-2-butene 0.63 0.76 0.55 3.38 3.31 2.94 i-pentane 0.19 0.180.16 0.02 0.02 0.03 n-pentane 0.01 0.01 0.04 1.27 1.12 2.081,3-butadiene 2.11 2.29 2.45 3.64 3.52 3.45 methyl acetylene 0.17 n/an/a 0.41 0.37 0.37 t-2-pentene 0.16 0.13 0.12 0.12 0.12 0.132-methyl-2-butene 0.03 0.03 0.03 0.05 0.06 0.09 1-pentene 0.02 0.02 0.020.08 0.10 0.12 c-2-pentene 0.11 0.10 0.09 0.08 0.09 0.11 pentadiene 10.00 0.00 0.00 0.05 0.08 0.14 pentadiene 2 0.01 0.03 0.02 0.23 0.36 0.53pentadiene 3 0.00 0.00 0.00 0.00 0.00 0.00 1,3-Cyclopentadiene 0.26 0.260.25 0.50 0.55 0.58 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00pentadiene 5 0.09 0.08 0.08 0.00 0.00 0.12 CO2 0.00 0.00 0.00 0.02 0.000.00 CO 0.00 0.00 0.00 0.06 0.06 0.03 Hydrogen 1.21 1.12 1.24 0.96 0.950.95 Unidentified 0.00 0.00 0.00 20.04  19.77  19.63  Olefin/AromaticsRatio 18.48  24.43  23.07  9.22 10.46  8.67 Total Aromatics 2.88 2.132.30 5.69 4.97 5.62 Propylene + − Ethylene 48.75  47.00  48.33  42.47 42.22  38.98  Ethylene/Propylene Ratio 1.65 1.50 1.67 1.88 1.92 2.24Carbon from Decoking, mg 96    44    32    90    71    23    *5% N2 wasalso added to facilitate steam generation. Analysis has been normalizedto exclude it. **100% accountability based on actual reactor effluentgas flow rate and gas chromatography analysis and calculation to givetheoretical mass of unidentified products.

The cracking results showed the same general trends that were seen inthe other cases, such as r-propylene and r-ethylene yield and totalaromatics increasing with a lower steam to hydrocarbon ratio due to thelonger residence time in the reactor. These runs were made to determinethe amount of carbon generated when a r-pyoil was cracked with propaneor natural gasoline. These were short runs but they was sufficientlyaccurate to see trends in coking. Cracking propane produced the leastcoking. The carbon produced ranged from 16 to 51 mg at 0.2 or lesssteam/ghydrocarbon ratio. Coking was the smallest at a 0.4steam/hydrocarbon ratio. In fact, only 1.5 mg of carbon was determinedafter decoking in Comparative 13. A much longer run time is needed toimprove accuracy. Since most commercial plants operate at a steam tohydrocarbon ratio of 0.3 or higher, the 51 mg obtained at 0.2 ratio maynot be unreasonable and may be considered a baseline for other feeds.For the r-pyoil/propane feed in Examples 53-55, increasing the ratiofrom 0.1 to 0.2 to 0.4 decreased the amount of carbon obtained from 96mg (Example 53) to 32 mg (Example 55). Even the 44 mg of carbon at a 0.2ratio (Example 54) was not unreasonable. Thus, using a 0.4 ratio for thecombined r-pyoil and propane feed inhibited coke formation similar tousing a 0.2-0.4 ratio for propane. Cracking r-pyoil with naturalgasoline required a 0.7 ratio (Example 58) to decrease the carbonobtained to the 20-50 mg range. At a 0.6 ratio, (Example 57) 71 mg ofcarbon was still obtained. Thus, operation of an 80/20 mixture ofnatural gasoline and r-pyoil should use a ratio of 0.7 or greater toprovide runtimes typical for operation of propane cracking.

Increasing the steam to hydrocarbon ratio decreased the amount of cokeformed in cracking propane, propane and r-pyoil, and natural gasolineand r-pyoil. A higher ratio was required as a heavier feedstock wascracked. Thus, propane required the lowest ratio to obtain low cokeformation. Cracking propane and r-pyoil required a ratio of about 0.4. Arange of 0.4 to 0.6 would be adequate to allow typical commercialruntimes between decoking. For the natural gasoline and r-pyoil mixture,even a higher ratio was required. In this case, a ratio of 0.7 or aboveis needed. Thus, operating at a steam to hydrocarbon ratio of 0.7 to 0.9would be adequate to allow typical commercial runtimes between decoking.

Example 59—Plant Test

About 13,000 gallons from tank 1012 of r-pyoil were used in the planttest as show in FIG. 12. The furnace coil outlet temperature wascontrolled either by the testing coil (Coil-A 1034 a or Coil-B 1034 b)outlet temperature or by the propane coil (Coil C 1034 c, coil D 1034 dthrough F) outlet temperature, depending on the objective of the test.In FIG. 12 the steam cracking system with r-pyoil 1010; 1012 is ther-pyoil tank; 1020 is the r-pyoil tank pump; 1024 a and 1226 b are TLE(transfer line exchanger); 1030 a, b,c is the furnace convectionsection; 1034 a, b, c, d are the coils in furnace firebox (the radiantsection); 1050 is the r-pyoil transfer line; 1052 a, b are the r-pyoilfeed that is added into the system; 1054 a, b, c, d are the regularhydrocarbon feed; 1058 a, b, c, d—are dilution steam; 1060 a and 1060 bare cracked effluent. The furnace effluent is quenched, cooled toambient temperature and separated out condensed liquid, the gas portionis sampled and analyzed by gas chromatograph.

For the testing coils, propane flow 1054 a and 1054 b were controlledand measured independently. Steam flow 1058 a and 1058 b were eithercontrolled by Steam/HC ratio controller or in an AUTO mode at a constantflow, depending on the objective of the test. In the non-testing coils,the propane flow was controlled in AUTO mode and steam flow wascontrolled in a ratio controller at Steam/Propane=0.3.

r-pyoil was obtained from tank 1012 through r-pyoil flow meters and flowcontrol valves into propane vapor lines, from where r-pyoil flowed alongwith propane into the convection section of the furnace and further downinto the radiant section also called the firebox. FIG. 12 shows theprocess flow.

The r-pyoil properties are shown in and Table 15 and FIG. 23. Ther-pyoil contained a small amount of aromatics, less than 8 wt. %, but alot of alkanes (more than 50%), thus making this material as a preferredfeedstock for steam cracking to light olefins. However, the r-pyoil hada wide distillation range, from initial boiling point of about 40° C. toan end point of about 400° C., as shown in Table 15 and FIGS. 24 and 25,covering a wide range of carbon numbers (C₄ to C₃₀ as shown in Table15). Another good characteristic of this r-pyoil is its low sulfurcontent of less than 100 ppm, but the r-pyoil had high nitrogen (327ppm) and chlorine (201 ppm) content. The composition of the r-pyoil bygas chromatography analysis is shown in Table 16.

TABLE 15 Properties of r-pyoil for plant test. Physical PropertiesDensity, 22.1° C., g/ml 0.768 Viscosity, 22.1 C., cP 1.26 InitialBoiling Point, ° C. 45 Flash Point, ° C. Below −1.1 Pour Point, ° C.−5.5 Impurities Nitrogen, ppmw 327 Sulfur, ppmw 74 Chlorine, ppmw 201Hydrocarbons, wt % Total Identified alkanes 58.8 Total IdentifiedAromatics 7.2 Total Identified Olefins 16.7 Total Identified Dienes 1.1Total Identified Hydrocarbons 83.5

TABLE 16 r-Pyoil composition. Component wt % Propane 0.17 1,3-Butadiene0.97 Pentene 0.40 Pentane 3.13 2-methyl-Pentene 2.14 2-methyl-Pentane2.46 Hexane 1.83 2,4-dimethylpentene 0.20 Benzene 0.175-methyl-1,3-cyclopentadiene 0.17 Heptene 1.15 Heptane 2.87 Toluene 1.074-methylheptane 1.65 Octene 1.51 Octane 2.77 2,4-dimethylheptene 1.522,4-dimethylheptane 3.98 Ethylbenzene 3.07 m,p-xylene 0.66 Styrene 1.11Mol. Weight = 140 1.73 Nonane 2.81 Cumene 0.96 Decene/methylstyrene 1.16Decane 3.16 Indene 0.20 Indane 0.26 C11-Alkene 1.31 C11-Alkane 3.29Napthanlene 0.00 C12-Alkene 1.29 C12-Alkane 3.21 C13-Alkene 1.19C13-Alkane 2.91 2-methylnapthalene 0.62 C14-Alkene 0.83 C14-Alkane 3.02acenapthalene 0.19 C15-alkene 0.86 C15-alkane 3.00 C16-Alkene 0.58C16-Alkane 2.66 C17-Alkene 0.46 C17-Alkane 2.42 C18-Alkene 0.32C18-Alkane 2.10 C19-Alkene 0.37 C19-Alkane 1.81 C20-Alkene 0.25C20-Alkane 1.53 C21-Alkene 0.00 C21-Alkane 1.28 C22-Alkane 1.10C23-Alkane 0.87 C24-Alkane 0.72 C25-Alkane 0.57 C26-Alkane 0.47C27-Alkane 0.36 c28-Alkane 0.28 c29-Alkane 0.22 C30-Alkane 0.17 TotalIdentified 83.5%

Before the plant test started, eight (8) furnace conditions (morespecifically speaking, eight conditions on the testing coils) werechosen. These included r-pyoil content, coil outlet temperature, totalhydrocarbon feeding rate, and the ratio of steam to total hydrocarbon.The test plan, objective and furnace control strategy are shown in Table17. “Float Mode” means the testing coil outlet temperature is notcontrolling the furnace fuel supply. The furnace fuel supply iscontrolled by the non-testing coil outlet temperature, or the coils thatdo not contain r-pyoil.

TABLE 17 Plan for the plant test of r-pyoil co-cracking with propane.Pyoil TOTAL, Pyoil/coil, Pyoil/coil, Stm/HC Propane/coil, Condition COT,° F. w % Py/C3H8 KLB/HR GPM lb/hr ratio klb/hr Base-line 1500 0 0.0006.0 0.00 0 0.3 6.00 1A Float Mode 5 0.053 6.0 0.79 300 0.3 5.70 1B FloatMode 10 0.111 6.0 1.58 600 0.3 5.40 1C & 2A Float Mode 15 0.176 6.0 2.36900 0.3 5.10 2B Lower by at 15 0.176 6.0 2.36 900 0.3 5.10 least 10 F.than the baseline 3A & 2C 1500 15 0.176 6.0 2.36 900 0.3 5.10 3B 1500 150.176 6.9 2.72 1035 0.3 5.87 4A 1500 15 0.176 6.0 2.36 900 0.4 5.10 4B1500 15 0.176 6.0 2.36 900 0.5 5.10 5A Float Mode 4.8 0.050 6.3 0.79 3000.3 6.00 5B At 2B COT 4.8 0.050 6.3 0.79 302 0.3 6.00

Effect of Addition of r-Pyoil

The results of r-Pyoil addition can be observed differently depending onhow propane flow, steam/HC ratio and furnace are controlled.Temperatures at crossover and coil outlet changed differently dependingon how propane flow and steam flow are maintained and how the furnace(the fuel supply to the firebox) was controlled. There were six coils inthe testing furnace. There were several ways to control the furnacetemperature via the fuel supply to the firebox. One of them was tocontrol the furnace temperature by an individual coil outlettemperature, which was used in the test. Both a testing coil and anon-testing coil were used to control the furnace temperature fordifferent test conditions.

Example 59.1—at Fixed Propane Flow, Steam/HC Ratio and Furnace FuelSupply (Condition 5A)

In order to check the r-pyoil 1052 a addition effect, propane flow andsteam/HC ratio were held constant, and furnace temperature was set tocontrol by a non-testing coil (Coil-C) outlet temperature. Then r-pyoil1052 a, in liquid form, without preheating, was added into the propaneline at about 5% by weight.

Temperature changes: After the r-pyoil 1052 a addition, the crossovertemperature dropped about 10° F. for A and B coil, COT dropped by about7° F. as shown in Table 18. There are two reasons that the crossover andCOT temperature dropped. One, there was more total flow in the testingcoils due to r-pyoil 1052 a addition, and two, r-pyoil 1052 aevaporation from liquid to vapor in the coils at the convection sectionneeded more heat thus dropping the temperature down. With a lower coilinlet temperature at the radiant section, the COT also dropped. The TLEexit temperature went up due to a higher total mass flow through the TLEon the process side.

Cracked gas composition change: As can be seen from the results in Table18, methane and r-ethylene decreased by about 1.7 and 2.1 percentagepoints, respectively, while r-propylene and propane increased by 0.5 and3.0 percentage points, respectively. The propylene concentrationincreased as did the propylene:ethylene ratio relative to the baselineof no pyoil addition. This was the case even though the propaneconcentration also increased. Others did not change much. The change inr-ethylene and methane was due to the lower propane conversion at thehigher flow rate, which was shown by a much higher propane content inthe cracked gas.

TABLE 18 Changes When Hydrocarbon Mass Flow Increases By Adding r-pyoilTo Propane At 5% At Constant Propane Flow, Steam/HC Ratio And FireboxCondition. Base- Base- 5A Add line line in Pyoil A&B Propane flow,klb/hr 11.87 11.86 11.85 A&B Pyoil flow, lb/hr 0 0 593 A&B Steam flow,lb/hr 3562 3556 3737 A&B total HC flow, klb/hr 11.87 11.86 12.44Pyoil/(poil + propane), % 0.0 0.0 4.8 Steam/HC, ratio 0.30 0.30 0.30 A&BCrossover T, F. 1092 1091 1081 A&B COT, F. 1499 1499 1492 A&B TLE ExitT, F. 691 691 698 A&B TLE Inlet, PSIG 10.0 10.0 10.0 A&B TLE Exit T,PSIG 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt % Hydrogen 1.26 1.391.29 Methane 18.83 18.89 17.15 Ethane 4.57 4.54 4.38 Ethylene 31.2531.11 28.94 Acetylene 0.04 0.04 0.04 Propane 20.13 21.25 24.15 Propylene17.60 17.88 18.36 MAPD 0.26 0.25 0.25 Butanes 0.11 0.12 0.15 Butadiene1.73 1.67 1.65 Butenes + CPD 1.41 1.41 1.62 Other C5s 0.42 0.37 0.40C6s+ 1.34 0.93 1.55 CO2 0.046 0.022 0.007 CO 1.001 0.134 0.061 Aver.M.W. 24.5 24.2 25.1

Example 59.2 at Fixed Total HC Flow, Steam/HC Ratio and Furnace FuelSupply (Conditions 1A, 1B, & 1C)

In order to check how the temperatures and crack gas composition changedwhen the total mass of hydrocarbons to the coil was held constant whilethe percent of r-pyoil 1052 a in the coil varied, steam flow to thetesting coil was held constant in AUTO mode, and the furnace was set tocontrol by a non-testing coil (Coil-C) outlet temp to allow the testingcoils to be in Float Mode. The r-pyoil 1052 a, in liquid form, withoutpreheating, was added into propane line at about 5, 10 and 15% byweight, respectively. When r-pyoil 1052 a flow was increased, propaneflow was decreased accordingly to maintain the same total mass flow ofhydrocarbon to the coil. Steam/HC ratio was maintained at 0.30 by aconstant steam flow.

Temperature Change: As the r-pyoil 1052 a content increased to 15%,crossover temperature dropped modestly by about 5° F., COT increasedgreatly by about 15° F., and TLE exit temperature just slightlyincreased by about 3° F., as shown in Table 19.

Cracked gas composition change: As r-pyoil 1052 a content in the feedincreased to 15%, methane, ethane, r-ethylene, r-butadiene and benzenein cracked gas all went up by about 0.5, 0.2, 2.0, 0.5, and 0.6percentage points, respectively. r-Ethylene/r-propylene ratio went up.Propane dropped significantly by about 3.0 percentage points, butr-propylene did not change much, as shown in Table 19A. These resultsshowed the propane conversion increased. The increased propaneconversion was due to the higher COT. When the total hydrocarbon feed tocoil, steam/HC ratio and furnace fuel supply are held constant, the COTshould go down when crossover temperature drops. However, what was seenin this test was opposite. The crossover temperature declined but COTwent up, as shown in Table 19a. This indicates that r-pyoil 1052 acracking does not need as much heat as propane cracking on the same massbasis.

TABLE 19A Variation of R-pyoil content and its effect on cracked gas andtemperatures (Steam/HC ratio and furnace firebox were held constant).Base- Base- 1A, 5% 1A, 5% 1B, 10% 1B, 10% 1C, 15% 1C, 15% line linePyoil Pyoil Pyoil Pyoil Pyoil pyoil A&B Propane flow, klb/hr 11.87 11.8611.25 11.25 10.66 10.68 10.06 10.07 A&B Pyoil Flow, lb/hr 0 0 537 5361074 1074 1776 1778 A&B Steam flow, lb/hr 3562 3556 3544 3543 3523 35233562 3560 A&B total HC flow, klb/hr 11.87 11.86 11.79 11.78 11.74 11.7511.84 11.85 Pyoil/(poil + propane), % 0.0 0.0 4.6 4.6 9.2 9.1 15.0 15.0Steam/HC, ratio 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A&B Crossover T,F 1092 1091 1092 1092 1090 1090 1088 1087 A&B COT, F 1499 1499 1503 15031509 1509 1514 1514 A&B TLE Exit T, F 691 691 692 692 692 692 693 693A&B TLE Inlet, PSIG 10.0 10.0 10.5 10.5 10.0 10.0 10.0 10.0 A&B TLE ExitT, PSIG 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt% wt % wt % wt % wt % wt % Hydrogen 1.26 1.39 1.40 1.32 1.33 1.28 1.311.18 Methane 18.83 18.89 18.96 18.74 19.31 19.08 19.61 19.16 Ethane 4.574.54 4.59 4.69 4.70 4.81 4.67 4.85 Ethylene 31.25 31.11 31.52 31.6232.50 32.63 33.06 33.15 Acetylene 0.04 0.04 0.04 0.04 0.05 0.05 0.050.05 Propane 20.13 21.25 20.00 19.95 18.58 18.65 16.97 17.54 Propylene17.60 17.88 17.85 17.86 17.79 17.85 17.58 17.81 MAPD 0.26 0.25 0.27 0.270.29 0.29 0.30 0.30 Butanes 0.11 0.12 0.11 0.11 0.10 0.10 0.10 0.10Butadiene 1.73 1.67 1.86 1.86 2.04 2.03 2.23 2.17 Butenes + CPD 1.411.41 1.52 1.52 1.59 1.57 1.67 1.65 Other C5s 0.42 0.37 0.38 0.38 0.380.37 0.40 0.39 C6s+ 1.34 0.93 1.37 1.50 1.24 1.21 1.95 1.56 CO2 0.0460.022 0.012 0.016 0.011 0.011 0.007 0.008 CO 1.001 0.134 0.107 0.1070.085 0.088 0.086 0.084 Aver. M.W. 24.5 24.2 24.2 24.4 24.2 24.4 24.224.6

Example 59.3 at Constant COT and Steam/HC Ratio (Conditions 2B, & 5B)

In the previous test and comparison, effect of r-pyoil 1052 a additionon cracked gas composition was influenced not only by r-pyoil 1052 acontent but also by the change of COT because when r-pyoil 1052 a wasadded, COT changed accordingly (it was set to Float Mode). In thiscomparison test, COT was held constant. The test conditions and crackedgas composition are listed in Table 19B. By comparing the data in Table19B, the same trend in cracked gas composition was found as in the caseExample 59.2. When r-pyoil 1052 a content in the hydrocarbon feed wasincreased, methane, ethane, r-ethylene, r-butadiene in cracked gas wentup, but propane dropped significantly while r-propylene did not changemuch.

TABLE 19B Changing r-Pyoil 1052a content in HC feed at constant coiloutlet temperature. 5B, Pyoil 2B, 15% 2B, 15% 5% @low T Pyoil Pyoil A&BPropane flow, 11.85 10.07 10.07 klb/hr A&B Pyoil Flow, lb/hr 601 17781777 A&B Steam flow, lb/hr 3738 3560 3559 A&B total HC flow, 12.45 11.8511.85 klb/hr Pyoil/(poil + 4.8 15.0 15.0 propane), % Steam/HC, ratio0.30 0.30 0.30 A&B Crossover T, F. 1062 1055 1059 A&B COT, F. 1478 14791479 A&B TLE Exit T, F. 697 688 688 A&B TLE Inlet, PSIG 10.0 10.0 10.0A&B TLE Exit T, PSIG 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt %Hydrogen 1.20 1.12 1.13 Methane 16.07 16.60 16.23 Ethane 4.28 4.81 4.65Ethylene 27.37 29.33 28.51 Acetylene 0.03 0.04 0.04 Propane 27.33 24.0125.51 Propylene 18.57 18.45 18.59 MAPD 0.23 0.27 0.25 Butanes 0.17 0.140.16 Butadiene 1.50 1.94 1.76 Butenes + CPD 1.63 1.65 1.73 Other C5s0.40 0.35 0.35 C6s+ 1.17 1.21 1.03 CO2 0.007 0.010 0.007 CO 0.047 0.0650.054 Aver. M.W. 25.8 25.7 25.9 C2H4/C3H6, wt/wt 1.47 1.59 1.53

Example 59.4 Effect of COT on Effluent Composition with R-Pyoil 1052 ain Feed (Conditions 1C, 2B, 2C, 5A & 5B)

r-Pyoil 1052 a in the hydrocarbon feed was held constant at 15% for 2B,and 2C. r-pyoil for 5A and 5B were reduced to 4.8%. The totalhydrocarbon mass flow and steam to HC ratio were both held constant.

On cracked gas composition. When COT increased from 1479° F. to 1514° F.(by 35° F.), r-ethylene and r-butadiene in the cracked gas went up byabout 4.0 and 0.4 percentage points, respectively, and r-propylene wentdown by about 0.8 percentage points, as shown in Table 20.

When r-pyoil 1052 a content in the hydrocarbon feed was reduced to 4.8%,the COT effect on the cracked gas composition followed the same trend asthat with 15% r-Pyoil 1052 a.

TABLE 20 Effect of COT on cracked gas composition. (Steam/HC ratio,R-pyoil 1052a content in the feed and total hydrocarbon mass flow wereall held constant) 1C, 1C, 2B, 2B, 2C, 2C, 5A, Add in 5B, Pyoil 15%Pyoil 15% pyoil 15% Pyoil 15% Pyoil 15% Pyoil 15% Pyoil Pyoil 5% to C₃H₈5%@ low T A&B Propane flow, klb/hr 10.06 10.07 10.07 10.07 10.07 10.0611.85 11.85 A&B Pyoil Flow, lb/hr 1776 1778 1778 1777 1777 1776 593 601A&B Steam flow, lb/hr 3562 3560 3560 3559 3560 3559 3737 3738 A&B totalHC flow, klb/hr 11.84 11.85 11.85 11.85 11.84 11.84 12.44 12.45Pyoil/(poil + propane), % 15.0 15.0 15.0 15.0 15.0 15.0 4.8 4.8Steam/HC, ratio 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A&B Crossover T,F 1088 1087 1055 1059 1075 1076 1081 1062 A&B COT, F 1514 1514 1479 14791497 1497 1492 1478 A&B TLE Exit T, F 693 693 688 688 690 691 698 697A&B TLE Inlet, PSIG 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 A&B TLE ExitT, PSIG 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt% wt % wt % wt % wt % wt % Hydrogen 1.31 1.18 1.12 1.13 1.26 1.25 1.291.20 Methane 19.61 19.16 16.60 16.23 18.06 17.87 17.15 16.07 Ethane 4.674.85 4.81 4.65 4.72 4.75 4.38 4.28 Ethylene 33.06 33.15 29.33 28.5131.03 30.73 28.94 27.37 Acetylene 0.05 0.05 0.04 0.04 0.04 0.04 0.040.03 Propane 16.97 17.54 24.01 25.51 21.17 21.10 24.15 27.33 Propylene17.58 17.81 18.45 18.59 18.29 18.30 18.36 18.57 MAPD 0.30 0.30 0.27 0.250.27 0.28 0.25 0.23 Butanes 0.10 0.10 0.14 0.16 0.13 0.13 0.15 0.17Butadiene 2.23 2.17 1.94 1.76 1.87 1.99 1.65 1.50 Butenes + CPD 1.671.65 1.65 1.73 1.71 1.77 1.62 1.63 Other C5s 0.40 0.39 0.35 0.35 0.370.40 0.40 0.40 C6s+ 1.95 1.56 1.21 1.03 1.00 1.30 1.55 1.17 CO2 0.0070.008 0.010 0.007 0.009 0.009 0.007 0.007 CO 0.086 0.084 0.065 0.0540.070 0.072 0.061 0.047 Aver. M.W. 24.2 24.6 25.7 25.9 24.8 24.9 25.125.8

Example 59.5 Effect of Steam/HC Ratio (Conditions 4A & 4B)

Steam/HC ratio effect is listed in Table 21A. In this test, r-pyoil 1052a content in the feed was held constant at 15%. COT in the testing coilswas held constant in SET mode, while the COTs at non-testing coils wereallowed to float. Total hydrocarbon mass flow to each coil was heldconstant.

On temperature. When steam/HC ratio was increased from 0.3 to 0.5, thecrossover temperature dropped by about 17° F. since the total flow inthe coils in the convection section increased due to more dilutionsteam, even though the COT of the testing coil was held constant. Due tothe same reason, TLE exit temperature went up by about 13 F.

On cracked gas composition. In the cracked gas, methane and r-ethylenewere reduced by 1.6 and 1.4 percentage points, respectively, and propanewas increased by 3.7 percentage points. The increased propane in thecracked gas indicated propane conversion dropped. This was due to,firstly, a shorter residence time, since in the 4B condition, the totalmoles (including steam) going into the coils was about 1.3 times of thatin 2° C. condition (assuming the average molecular weight of r-pyoil1052 a was 160), and secondly, to the lower crossover temperature whichwas the inlet temperature for the radiant coil, making the averagecracking temperature lower.

TABLE 21A Effect of steam/HC ratio. (r-Pyoil in the HC feed at 15%,total hydrocarbon mass flow and COT were held constant). 2C, 15% 2C, 15%4A, Stm 4B, Stm Pyoil Pyoil ratio 0.4 ratio 0.5 A&B Propane flow, 10.0710.06 10.08 10.08 klb/hr A&B Pyoil Flow, lb/hr 1777 1776 1778 1778 A&BSteam flow, lb/hr 3560 3559 4748 5933 A&B total HC flow, 11.84 11.8411.85 11.85 klb/hr Pyoil/(poil + 15.0 15.0 15.0 15.0 propane), %Steam/HC, ratio 0.30 0.30 0.40 0.50 A&B Crossover T, F. 1075 1076 10631058 A&B COT, F. 1497 1497 1498 1498 A&B TLE Exit T, F. 690 691 698 703A&B Feed Pres, PSIG 69.5 69.5 67.0 67.0 A&B TLE Inlet, PSIG 10.0 10.010.0 11.0 A&B TLE Exit T, PSIG 9.0 9.0 9.0 9.0 Cracked Gas Product wt %wt % wt % wt % Hydrogen 1.26 1.25 0.87 1.12 Methane 18.06 17.87 16.3016.18 Ethane 4.72 4.75 4.55 4.38 Ethylene 31.03 30.73 29.92 29.52Acetylene 0.04 0.04 0.05 0.05 Propane 21.17 21.10 23.40 24.88 Propylene18.29 18.30 18.67 18.49 MAPD 0.27 0.28 0.29 0.28 Butanes 0.13 0.13 0.150.16 Butadiene 1.87 1.99 2.01 1.85 Butenes + CPD 1.71 1.77 1.89 1.81Other C5s 0.37 0.40 0.43 0.37 C6s+ 1.00 1.30 1.38 0.84 CO2 0.009 0.0090.026 0.008 CO 0.070 0.072 0.070 0.061

On cracked gas composition. In the cracked gas, methane and r-ethylenewere reduced by 1.6 and 1.4 percentage points, respectively, and propanewas increased

Renormalized cracked gas composition. In order to see what the lighterproduct composition could be if ethane and propane in the cracked gaswould be recycled, the cracked gas composition in Table 21A wasrenormalized by taking off propane or ethane+propane, respectively. Theresulting composition is listed in Table 21B. It can be seen, olefin(r-ethylene+r-propylene) content went up with steam/HC ratio.

TABLE 21B Renormalized cracked gas composition. (R-pyoil in the HC feedat 15%, total hydrocarbon mass flow and COT were held constant). 2C, 15%4A, Stm 4B, Stm Pyoil ratio 0.4 ratio 0.5 A&B Propane flow, 10.07 10.0810.08 klb/hr Pyoil/(poil + 15.0 15.0 15.0 propane), % Steam/HC, ratio0.30 0.40 0.50 A&B Crossover T, F. 1075 1063 1058 A&B COT, F. 1497 14981498 Renorm. w/o Propane wt % wt % wt % Hydrogen 1.60 1.14 1.49 Methane22.91 21.28 21.54 Ethane 5.99 5.94 5.83 Ethylene 39.36 39.06 39.29Acetylene 0.05 0.06 0.06 Propylene 23.21 24.37 24.62 MAPD 0.34 0.38 0.38Butanes 0.17 0.20 0.21 Butadiene 2.37 2.63 2.46 Butenes + CPD 2.16 2.472.41 Other C5s 0.46 0.56 0.50 C6s+ 1.27 1.80 1.12 CO2 0.011 0.033 0.010CO 0.089 0.091 0.081 C2H4 + C3H6 62.57 63.43 63.91 Renorm. w/o C2H6 +C3H8 wt % wt % wt % Hydrogen 1.70 1.21 1.58 Methane 24.37 22.62 22.87Ethylene 41.87 41.52 41.73 Acetylene 0.06 0.06 0.06 Propylene 24.6925.91 26.15 MAPD 0.36 0.40 0.40 Butanes 0.18 0.21 0.22 Butadiene 2.522.79 2.61 Butenes + CPD 2.30 2.62 2.55 Other C5s 0.49 0.60 0.53 C6s+1.35 1.91 1.19 CO2 0.012 0.035 0.011 CO 0.094 0.097 0.086 C2H4 + C3H666.55 67.43 67.87

Effect of total hydrocarbon feed flow (Conditions 2C & 3B) An increasein total hydrocarbon flow to the coil means a higher throughput but ashorter residence time, which reduces conversion. With r-pyoil 1052 a at15% in the HC feed, a 10% increase of the total HC feed brought about aslight increase in the propylene:ethylene ratio along with an increasein the concentration of propane without a change in ethane, when COT washeld constant. Other changes were seen on methane and r-ethylene. Eachdropped about 0.5-0.8 percentage points. The results are listed in Table22.

TABLE 22 Comparison of more feed to coil (Steam/HC ratio = 0.3, COT isheld constant at 1497 F.). 2C, 15% 2C, 15% 3B, 10% 3B, 10% Pyoil Pyoilmore FD more FD A&B Propane flow, 10.07 10.06 11.09 11.09 klb/hr A&BPyoil Flow, lb/hr 1777 1776 1956 1957 A&B Steam flow, lb/hr 3560 35593916 3916 A&B total HC flow, 11.84 11.84 13.04 13.05 klb/hrPyoil/(poil + 15.0 15.0 15.0 15.0 propane), % Steam/HC, ratio 0.30 0.300.30 0.30 A&B Crossover T, F. 1075 1076 1066 1065 A&B COT, F. 1497 14971497 1497 A&B TLE Exit T, F. 690 691 698 699 A&B TLE Inlet, PSIG 10.010.0 10.3 10.3 A&B TLE Exit T, PSIG 9.0 9.0 9.0 9.0 Cracked Gas Productwt % wt % wt % wt % Hydrogen 1.26 1.25 1.19 1.24 Methane 18.06 17.8717.23 17.31 Ethane 4.72 4.75 4.76 4.79 Ethylene 31.03 30.73 30.02 29.95Acetylene 0.04 0.04 0.04 0.04 Propane 21.17 21.10 22.51 22.31 Propylene18.29 18.30 18.44 18.28 MAPD 0.27 0.28 0.28 0.28 Butanes 0.13 0.13 0.150.14 Butadiene 1.87 1.99 1.93 1.95 Butenes + CPD 1.71 1.77 1.82 1.82Other C5s 0.37 0.40 0.41 0.42 C6s+ 1.00 1.30 1.15 1.39 CO2 0.009 0.0090.009 0.008 CO 0.070 0.072 0.065 0.066

r-pyoil 1052 a is successfully co-cracked with propane in the same coilon a commercial scale furnace.

1. (canceled)
 2. A method of making a recycle content oxo glycolcomposition (“r-OG”), said method comprising hydroformylating a recyclecontent olefin composition at least a portion of which is deriveddirectly or indirectly from pyrolyzing a recycled waste with syngas toform a recycle content aldehyde (r-AD) and then reacting at least aportion of the r-AD in the presence of a catalyst to produce an oxoglycol effluent comprising r-oxo glycol (“r-OG”).
 3. The methodaccording to claim 2, wherein the oxo glycol effluent is produced byhydrogenating at least a portion of the r-AD to produce an oxo glycoleffluent comprising r-oxo glycol (“r-OG”).
 4. (canceled)
 5. A method ofmaking oxo glycol, said method comprising: a. an oxo glycol manufacturerobtaining an olefin or an aldehyde composition from a supplier andeither: i. from said supplier, also obtaining a pyrolysis recyclecontent allotment or ii. from any person or entity, obtaining apyrolysis recycle content allotment without a supply of an olefin oraldehyde composition from said person or entity transferring saidpyrolysis recycle content allotment; and b. said oxo glycol manufacturermaking an oxo glycol composition (“OG”) from any olefin or aldehydecomposition obtained from any source; and c. either: i. applying saidpyrolysis recycle content allotment to OG made by the supply of olefinor aldehyde obtained in step (a); or ii. applying said pyrolysis recyclecontent allotment to OG not made by the supply of olefin or aldehydeobtained in step (a), or iii. depositing said pyrolysis recycle contentallotment into a recycle inventory from which is deducted a recyclecontent value and applying at least a portion of said value to:
 1. OG tothereby obtain r-OG, or
 2. to a compound or composition other than OG,or
 3. both; whether or not the recycle content value is obtained from apyrolysis recycle content allotment obtained in step a(i) or step a(ii).6. A method of making a recycle content oxo glycol composition (“r-OG”),said method comprising: a. reacting any olefin or aldehyde compositionin a synthetic process to make a oxo glycol composition (“OG”); and b.applying a recycle content value to at least a portion of said OG tothereby obtain a recycle content oxo glycol composition (“r-OG”); and c.optionally, obtaining said recycle content value by deducting at least aportion of said recycle content value from a recycle inventory, furtheroptionally said recycle inventory also containing a pyrolysis recyclecontent allotment or a pyrolysis recycle content allotment deposithaving been made into the recycle inventory prior to the deduction; andd. optionally communicating to a third party that said r-OG has recyclecontent or is obtained or derived from recycled waste.
 7. (canceled) 8.The method according to claim 6, said method further comprising: a.pyrolyzing a pyrolysis feed comprising a recycled waste material tothereby form a pyrolysis effluent comprising recycle pyoil (r-pyoil)and/or a recycle pygas (“r-pygas”); b. optionally cracking a crackerfeed comprising at least a portion of the r-pyoil to thereby produce acracker effluent comprising r-olefins; or optionally cracking a crackerfeed without r-pyoil to make olefins and applying a recycle contentvalue to the olefins so made by deducting a recycle content value from arecycle inventory and applying it to the olefins to make r-olefins; andc. reacting any olefin volume in a synthetic process to make an aldehydecomposition; and d. reacting at least a portion of any aldehydecomposition in a synthetic process to make an oxo glycol composition;and e. applying a recycle content value to at least a portion of saidoxo glycol composition based on: i. feeding a pyrolysis recycle contentolefin (“pr-olefin”) or recycle aldehyde composition (“pr-AD”) as afeedstock or ii. depositing at least a portion of an allotment obtainedfrom any one or more of steps a) or b) into a recycle inventory anddeducting from said inventory a recycle content value and applying atleast a portion of said value to OG to thereby obtain said r-OG. 9.-16.(canceled)
 17. A recycle content oxo glycol composition (“r-OG”)obtained by the method according to claim
 6. 18. The method according toclaim 6, wherein said recycle content value is derived directly orindirectly from cracking r-pyoil or obtained from r-pygas.
 19. Themethod according to claim 6, wherein said recycle content value isderived directly or indirectly from cracking r-pyoil in a gas fedcracker furnace. 20.-21. (canceled)
 22. The method according to claim 6,wherein the olefin or aldehyde composition is fed to a reaction vesseland said olefin or aldehyde composition does not contain recyclecontent. 23.-25. (canceled)
 26. The method according to claim 6, whereinthe oxo glycol is made by an oxo glycol manufacturer and the recyclecontent is apportioned among products made by a oxo glycol manufactureror the products made by any one entity or a combinations of entitiesamong the Family of Entities of which the oxo glycol manufacturer is apart, and wherein the method for apportioning is an asymmetricdistribution of recycle content values among their product(s), andoptionally at least one of the products is oxo glycol.
 27. (canceled)28. The method according to claim 6, wherein the oxo glycol is made byan oxo glycol manufacturer and the recycle content is apportioned amongproducts made by a OG manufacturer or the products made by any oneentity or a combinations of entities among the Family of Entities ofwhich the OG manufacturer is a part, and wherein the method forapportioning is applied symmetrically or asymmetrically across acombination of OG and other products.
 29. The method according to claim6, wherein the AD is supplied by an AD supplier that transfers a recyclecontent allotment to the OG manufacturer and a supply of AD to the OGmanufacturer.
 30. The method according to claim 6, wherein the recyclecontent allotment is not associated with the AD supplied. 31.-32.(canceled)
 33. The method according to claim 6, wherein the AD issupplied by an AD supplier that transfers a recycle content allotment tothe OG manufacturer and a supply of AD to the OG manufacturer, and therecycle content allotment is associated with AD made by the supplier.34. The method according to claim 6, wherein the AD supplied is r-AD andat least a portion of the recycle content allotment being transferred isthe recycle content in the r-AD supplied. 35.-38. (canceled)
 39. Themethod according to claim 6, wherein the recycle content value appliedto OG is drawn from a recycle inventory that is derived directly orindirectly from the pyrolysis of recycled waste.
 40. (canceled)
 41. Themethod according to claim 6, wherein an OG manufacturer or a person orentity among its Family of Entities obtains a supply of AD and anallotment, and at least a portion of the allotment is either: a. appliedto OG made from the AD supplied; b. applied to OG not made by the supplyof AD; or c. deposited into a recycle inventory from which is deducted arecycle content value and applying at least a portion of the recyclecontent value to: i. OG to thereby obtain r-OG, or ii. to a compound orcomposition other than OG, or iii. both; or d. deposited into a recycleinventory and stored. 42.-51. (canceled)
 52. The method according toclaim 6, wherein: a. an olefin supplier either: i. cracks a crackerfeedstock comprising recycle pyoil to make an olefin composition atleast a portion of which is obtained by cracking said recycle pyoil(r-olefin), or ii. makes a pygas at least a portion of which is obtainedby pyrolyzing a recycled waste stream (r-pygas), or iii. both; and b. anoxo glycol manufacturer: i. obtains an allotment derived directly orindirectly with said r-olefin or said r-pygas from the supplier or athird-party transferring said allotment, ii. makes oxo glycol fromolefin or aldehyde, and iii. associates at least a portion of theallotment with at least a portion of the oxo glycol, whether or not theolefin or aldehyde used to make the oxo glycol contains r-olefin orr-aldehyde.
 53. The method according to claim 6, comprising: a. making ar-olefin by either cracking r-pyoil or separating an olefin fromr-pygas; and b. converting at least a portion of the r-olefin in asynthetic process to make an aldehyde, and c. converting at least aportion of any or said olefin or aldehyde to oxo glycol; and d. applyinga recycle content value to said oxo glycol to make a r-OG; and e.optionally, also making a r-pyoil or r-pygas or both by pyrolyzing arecycle feedstock. 54.-55. (canceled)
 56. The method according to claim6, comprising: a. oxo glycol (“OG”), and b. an identifier associatedwith said oxo glycol, said identifier being a representation that saidoxo glycol has recycle content or is made from a source having recyclecontent. 57.-58. (canceled)